Polyethylene compositions and films prepared therefrom

ABSTRACT

A polyethylene composition comprising from about 0.5 to about 20 wt % of alpha-olefin derived units other than ethylene-derived units, with the balance including ethylene-derived units, total internal unsaturations (Vy1+Vy2+T1) of from about 0.10 to about 0.40 per 1000 carbon atoms, an MI of from about 0.1 to about 6 g/10 min, an HLMI of from about 5.0 to about 40 g/10 min, a density of from about 0.890 to about 0.940 g/ml, a Tw1-Tw2 value of from about −25 to about −20° C., an Mw1/Mw2 value of from about 1.2 to about 2.0, an Mw/Mn of from about 4.5 to about 12, an Mz/Mw of from about 2.0 to about 3.0, an Mz/Mn of from about 7.0 to about 20, and a g′(vis) greater than 0.90.

CROSS-REFERENCE OF RELATED APPLICATIONS

This application is a national state filing of Patent Cooperation TreatyApplication No. PCT/US2018/039081, which claims the benefit of Ser. No.62/541,372, filed Aug. 4, 2017, and Ser. No. 62/541,360 filed Aug. 4,2017, the disclosures of which are hereby incorporated by reference intheir entireties.

FIELD OF INVENTION

This application relates to polyethylene compositions having uniquecharacteristics, which characteristics give rise to films having anadvantageous balance of toughness, stiffness, processability, andoptical qualities.

BACKGROUND OF INVENTION

Ethylene alpha-olefin (polyethylene) copolymers are typically producedin a low pressure reactor, utilizing, for example, solution, slurry, orgas phase polymerization processes. Polymerization takes place in thepresence of catalyst systems such as those employing, for example, aZiegler-Natta catalyst, a chromium based catalyst, a metallocenecatalyst, or combinations thereof.

A number of catalyst compositions containing single site, e.g.,metallocene, catalysts have been used to prepare polyethylenecopolymers, producing relatively homogeneous copolymers at goodpolymerization rates. In contrast to traditional Ziegler-Natta catalystcompositions, single site catalyst compositions, such as metallocenecatalysts, are catalytic compounds in which each catalyst moleculecontains one or only a few polymerization sites. Single site catalystsoften produce polyethylene copolymers that have a narrow molecularweight distribution. Although there are single site catalysts that canproduce broader molecular weight distributions, these catalysts oftenshow a narrowing of the molecular weight distribution as the reactiontemperature is increased, for example, to increase production rates.Further, a single site catalyst will often incorporate comonomer amongthe molecules of the polyethylene copolymer at a relatively uniformrate. The molecular weight distribution (MWD) and the amount ofcomonomer incorporation can be used to determine a SCBD.

For an ethylene alpha-olefin copolymer, short chain branching (SCB) on apolymer chain is typically created through comonomer incorporationduring polymerization. Short chain branch distribution (SCBD) refers tothe distribution of short chain branches within a molecule or amongdifferent molecules that comprise the polyethylene polymer. When theamount of SCB varies among the polyethylene molecules, the resin is saidto have a “broad” SCBD. When the amount of SCB is similar among thepolyethylene molecules of different chain lengths, the SCBD is said tobe “narrow.”

SCBD is known to influence the properties of copolymers, for example,stiffness, toughness, extractable content, environmental stress crackresistance, and heat sealing, among other properties. SCBD of apolyolefin may be readily measured by methods known in the art, forexample, Temperature Raising Elution Fractionation (TREF) orCrystallization Analysis Fractionation (CRYSTAF).

It is generally known in the art that a polyolefin's MWD and SCBD islargely dictated by the type of catalyst used and is often invariablefor a given catalyst system. Ziegler-Nana catalysts and chromium basedcatalysts produce polymers with broad SCBD, whereas metallocenecatalysts normally produce polymers with narrow SCBD. It has been longobserved in the industry that there are trade-off paradigms among thedifferent product attributes; most noticeably among stiffness,toughness, and processability (S/T/P). Since the introduction ofmetallocene in 1990s, some of such paradigms have been relaxedsignificantly with careful manipulations of molecular structure andcomposition in the product.

Polymers having a broad orthogonal composition distribution (BOCD) inwhich the comonomer is incorporated preferentially in the high molecularweight chains can lead to improved physical properties, for example,stiffness, toughness, processability, and environmental stress crackresistance (ESCR), among others. Because of the improved physicalproperties of polymers with orthogonal composition distributions neededfor commercially desirable products, there exists a need for controlledtechniques for forming polyethylene copolymers having a broad orthogonalcomposition distribution.

It is therefore sought to provide ethylene polymers having the uniqueproperties of high stiffness, high toughness and good opticalproperties.

SUMMARY OF INVENTION

In one aspect, a polyethylene composition is provided that comprises aplurality of polymeric molecules, where each molecule includesethylene-derived units and optionally alpha-olefin derived units otherthan ethylene-derived units, said polyethylene composition beingcharacterized by including from about 0.5 to about 20 wt % ofalpha-olefin derived units other than ethylene-derived units, with thebalance including ethylene-derived units, total internal unsaturations(Vy1+Vy2+T1) of from about 0.10 to about 0.40 per 1000 carbon atoms, anMI of from about 0.1 to about 6 g/10 min, an HLMI of from about 5.0 toabout 40 g/10 min, a density of from about 0.890 to about 0.940 g/ml, aTw₁-Tw₂ value of from about −25 to about −20° C., an Mw₁/Mw₂ value offrom about 1.2 to about 2.0, an Mw/Mn of from about 4.5 to about 12, anMz/Mw of from about 2.0 to about 3.0, an Mz/Mn of from about 7.0 toabout 20, and a g′_((vis)) greater than 0.90.

In another aspect, a blown polyethylene film is provided that comprisesa polyethylene composition including a plurality of polymeric molecules,where each molecule includes ethylene-derived units and optionally C3 toC12 alpha-olefin derived units, said polyethylene composition beingcharacterized by including from about 0.5 to about 20 wt % ofalpha-olefin derived units other than ethylene-derived units, with thebalance including ethylene-derived units, total internal unsaturations(Vy1+Vy2+T1) of from about 0.10 to about 0.40 per 1000 carbon atoms, anMI of from about 0.1 to about 6 g/10 min, an HLMI of from about 5.0 toabout 40 g/10 min, a density of from about 0.890 to about 0.940 g/ml, aTw₁-Tw₂ value of from about −25 to about −20° C., an Mw₁/Mw₂ value offrom about 1.2 to about 2.0, an Mw/Mn of from about 4.5 to about 12, anMz/Mw of from about 2.0 to about 3.0, an Mz/Mn of from about 7.0 toabout 20, and a g′_((vis)) greater than 0.90, where said blown film ischaracterized by a Dart Drop Impact (DI) that is greater than 300 g/mil,a haze of less than 30%, and a machine-direction tear resistance that isgreater than 120 g/mil.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A and 1B are plots that help illustrate how data fromCross-Fractionation Chromatography was used to define characteristics ofthe polyethylene compositions.

FIG. 2 is a plot showing important differences in MWD/SCBD combinationsof polyethylene compositions.

FIG. 3 is a graphical representation of Average Film modulus as afunction of Resin Density for films prepared from various polyethylenecompositions.

DETAILED DESCRIPTION OF THE PRESENT INVENTION

Definitions

For purposes of this invention and the claims thereto, a “catalystsystem” is a combination of at least two catalyst compounds, anactivator, and a support material. The catalyst systems may furthercomprise one or more additional catalyst compounds. The terms “mixedcatalyst system,” “dual catalyst system,” “mixed catalyst,” and“supported catalyst system” may be used interchangeably herein with“catalyst system.” For the purposes of this invention and the claimsthereto, when catalyst systems are described as comprising neutralstable forms of the components, it is well understood by one of ordinaryskill in the art, that the ionic form of the component is the form thatreacts with the monomers to produce polymers.

The term “complex” is used to describe molecules in which an ancillaryligand is coordinated to a central transition metal atom. The ligand isbulky and stably bonded to the transition metal so as to maintain itsinfluence during use of the catalyst, such as polymerization. The ligandmay be coordinated to the transition metal by covalent bond and/orelectron donation coordination or intermediate bonds. The transitionmetal complexes are generally subjected to activation to perform theirpolymerization function using an activator which is believed to create acation as a result of the removal of an anionic group, often referred toas a leaving group, from the transition metal. “Complex,” as usedherein, is also often referred to as “catalyst precursor,”“pre-catalyst,” “catalyst,” “catalyst compound,” “metal compound,”“transition metal compound,” or “transition metal complex.” These wordsare used interchangeably. “Activator” and “cocatalyst” are also usedinterchangeably.

The terms “hydrocarbyl radical,” “hydrocarbyl” and “hydrocarbyl group”are used interchangeably throughout this document. Likewise the terms“group,” “radical,” and “substituent” are also used interchangeably inthis document. For purposes of this invention, “hydrocarbyl radical” isdefined to be C₁-C₁₀₀ radicals, that may be linear, branched, or cyclic,and when cyclic, aromatic or non-aromatic.

For purposes of this invention and claims thereto, unless otherwiseindicated, the term “substituted” means that a hydrogen group has beenreplaced with a heteroatom, or a heteroatom containing group. Forexample, substituted hydrocarbyl radicals are radicals in which at leastone hydrogen atom of the hydrocarbyl radical has been substituted withat least one functional group such as Cl, Br, F, I, NR*₂, OR*, SeR*,TeR*, PR*₂, AsR*₂, SbR*₂, SR*, BR*₂, SiR*₃, GeR*₃, SnR*₃, PbR*₃ and thelike (where R* is H or a C₁ to C₂₀ hydrocarbyl group), or where at leastone heteroatom has been inserted within a hydrocarbyl ring.

The term “ring atom” means an atom that is part of a cyclic ringstructure. By this definition, a benzyl group has six ring atoms andtetrahydrofuran has 5 ring atoms.

A “ring carbon atom” is a carbon atom that is part of a cyclic ringstructure. By this definition, a benzyl group has six ring carbon atomsand para-methylstyrene also has six ring carbon atoms.

The term “aryl” or “aryl group” means a six carbon aromatic ring and thesubstituted variants thereof, including but not limited to, phenyl,2-methyl-phenyl, xylyl, 4-bromo-xylyl. Likewise, heteroaryl means anaryl group where a ring carbon atom (or two or three ring carbon atoms)has been replaced with a heteroatom, preferably, N, O, or S.

A “heterocyclic ring” is a ring having a heteroatom in the ringstructure as opposed to a heteroatom substituted ring where a hydrogenon a ring atom is replaced with a heteroatom. For example,tetrahydrofuran is a heterocyclic ring and 4-N,N-dimethylamino-phenyl isa heteroatom substituted ring.

As used herein the term “aromatic” also refers to pseudoaromaticheterocycles which are heterocyclic substituents that have similarproperties and structures (nearly planar) to aromatic heterocyclicligands, but are not by definition aromatic; likewise, the term aromaticalso refers to substituted aromatics.

The term “continuous” means a system that operates without interruptionor cessation. For example, a continuous process to produce a polymerwould be one where the reactants are continually introduced into one ormore reactors and polymer product is continually withdrawn.

As used herein, the numbering scheme for the Periodic Table groups isthe new notation as set out in Chemical and Engineering News, 63(5), 27,(1985).

An “olefin,” is a linear, branched, or cyclic compound of carbon andhydrogen having at least one double bond. For purposes of thisspecification and the claims appended thereto, when a polymer orcopolymer is referred to as comprising an olefin, the olefin present insuch polymer or copolymer is the polymerized form of the olefin. Forexample, when a copolymer is said to have an “ethylene” content of 35 wt% to 55 wt %, it is understood that the mer unit in the copolymer isderived from ethylene in the polymerization reaction and said derivedunits are present at 35 wt % to 55 wt %, based upon the weight of thecopolymer. A “polymer” has two or more of the same or different merunits. A “homopolymer” is a polymer having mer units that are the same.A “copolymer” is a polymer having two or more mer units that aredifferent from each other. “Different” as used to refer to mer unitsindicates that the mer units differ from each other by at least one atomor are different isomerically. Accordingly, the definition of copolymer,as used herein, includes terpolymers and the like. An “ethylene polymer”or “ethylene copolymer” is a polymer or copolymer comprising at least 50mol % ethylene derived units, a “propylene polymer” or “propylenecopolymer” is a polymer or copolymer comprising at least 50 mol %propylene derived units, and so on.

For purposes of this invention and the claims thereto, an ethylenepolymer having a density of 0.86 g/cm³ or less is referred to as anethylene elastomer or elastomer; an ethylene polymer having a density ofmore than 0.86 to less than 0.910 g/cm³ is referred to as an ethyleneplastomer or plastomer; an ethylene polymer having a density of 0.910 to0.940 g/cm³ is referred to as a low density polyethylene; and anethylene polymer having a density of more than 0.940 g/cm³ is referredto as a high density polyethylene (HDPE). Density is determinedaccording to ASTM D 1505 using a density-gradient column on acompression-molded specimen that has been slowly cooled to roomtemperature (i.e., over a period of 10 minutes or more) and allowed toage for a sufficient time that the density is constant within +/−0.001g/cm³).

Polyethylene in an overlapping density range, i.e., 0.890 to 0.930g/cm³, typically from 0.915 to 0.930 g/cm³, which is linear and does notcontain long chain branching is referred to as “linear low densitypolyethylene” (LLDPE) and has been produced with conventionalZiegler-Natta catalysts, vanadium catalysts, or with metallocenecatalysts in gas phase reactors and/or in slurry reactors and/or insolution reactors. “Linear” means that the polyethylene has no longchain branches, typically referred to as a branching index (g′_(vis)) of0.97 or above, preferably 0.98 or above. Branching index, g′_(vis), ismeasured by GPC-4D as described below.

For the purposes of this invention, ethylene shall be considered anα-olefin.

As used herein, M_(n) is number average molecular weight, M_(w) isweight average molecular weight, and M_(z) is z average molecularweight, wt % is weight percent, and mol % is mole percent. Molecularweight distribution (MWD), also referred to as polydispersity index(PDI), is defined to be Mw divided by Mn. Unless otherwise noted, allmolecular weights (e.g., Mw, Mn, Mz) are reported in units of g/mol. Thefollowing abbreviations may be used herein: Me is methyl, Et is ethyl,t-Bu and ^(t)Bu are tertiary butyl, iPr and ^(i)Pr are isopropyl, Cy iscyclohexyl, THF (also referred to as thf) is tetrahydrofuran, Bn isbenzyl, Ph is phenyl, Cp is cyclopentadienyl, Cp* is pentamethylcyclopentadienyl, Ind is indenyl, Flu is fluorenyl, and MAO ismethylalumoxane.

Introduction

Embodiments of the invention are based, at least in part, on thediscovery of polyethylene compositions that are useful for preparingimproved polymeric films that demonstrate a desirable balance ofproperties such as stiffness, toughness, processability, and opticalproperties. And, it has been discovered that these advantageous filmproperties are linked, at least in part, to certain characteristics ofthe polyethylene composition. Moreover, it has unexpectedly beendiscovered that these characteristics serve to distinguish thesepolyethylene compositions from those polyethylene compositions that donot give rise to films with the advantageous properties. Accordingly,embodiments of the invention are directed toward novel polyethylenecompositions having specific characteristics and films prepared fromthese polyethylene compositions.

Characteristics of Composition

Comonomer Content

The polyethylene compositions of the present invention include aplurality of polyethylene polymeric molecules that include at least oneof polyethylene homopolymer and polyethylene copolymers, which arecopolymers including ethylene-derived units and alpha-olefin-derived. Inother words, the polyethylene copolymers are prepared from thepolymerization of ethylene and at least one alpha-olefin monomer otherthan ethylene. Unless otherwise stated, the term polyethylenecomposition will refer to a composition including at least one of apolyethylene homopolymer and a polyethylene copolymer. In particularembodiments, the composition includes both a polyethylene homopolymerand a polyethylene copolymer.

For purposes of this specification, alpha-olefin monomer other thanethylene may be referred to as C3 (i.e. propene) or higher alpha-olefin.In particular embodiments, the alpha-olefin includes a C3 to C12alpha-olefin. In one or more embodiments, the alpha-olefin monomer otherthan ethylene includes, but is not limited to, propylene, butene,hexene, octene, decene, and dodecene. In particular embodiments, thepolyethylene copolymers are prepared from the polymerization of ethyleneand butene, in other embodiments ethylene and hexane, and in otherembodiments ethylene and octene.

According to embodiments of the present invention, the polyethylenecompositions may be characterized by the amount of alpha-olefin-derivedunits, other than ethylene-derived units, within the composition. As theskilled person will appreciate, the amount of alpha-olefin-derived units(i.e. non-ethylene units) can be determined by 4D GPC analysis, whichanalysis is described herein.

In one or more embodiments, the polyethylene compositions may includegreater than 0.5, in other embodiments greater than 1, and in otherembodiments greater than 3 mole % alpha-olefin-derived units other thanethylene-derived units, with the balance including ethylene-derivedunits. In these or other embodiments, the polyethylene compositions mayinclude less than 20, in other embodiments less than 15, in otherembodiments less than 10, and in other embodiments less than 7 mole %alpha-olefin-derived units other than ethylene-derived units, with thebalance including ethylene-derived units. In one or more embodiments,the polyethylene composition of the present invention may include fromabout 0.5 to 20 mole %, in other embodiments from 1 to 15 mole %, and inother embodiments from 3 to 10 mole % alpha-olefin-derived units otherthan ethylene-derived units, with the balance including ethylene-derivedunits.

Internal Unsaturation

The polyethylene compositions of the present invention may becharacterized by their level of internal unsaturation structures.Internal (I) and terminal (T) unsaturation can be determined byemploying the techniques described in U.S. Publication No. 2017/0114167,which is incorporated herein by reference. Specifically, unsaturationsin a polymer are determined by ¹H NMR with reference to Macromolecules2014, 47, 3782 and Macromolecules 2005, 38, 6988, but in event ofconflict, Macromolecules 2014, 47, 3782 shall control. Peak assignmentsare determined referencing the solvent of tetrachloroethane-1,2 d₂ at5.98 ppm. The labels “Vy1”, “Vy2” and “Vy5” refer to proton resonancesattributed to the protons on double bonds within the polymer backbone.Internal unsaturations include unsaturation assigned to peaks Vy1 andVy2, which represent unsaturation without carbon substitution, and T1,which represents tri-substituted olefins or, stated another way,unsaturation with carbon substitution. ¹H NMR data is typicallycollected at 393K in a 10 mm probe using a Bruker spectrometer with a ¹Hfrequency of at least 400 MHz (available from Agilent Technologies,Santa Clara, Calif.). Data can be recorded using a maximum pulse widthof 45° C., 5 seconds between pulses and signal averaging 512 transients.Spectral signals are integrated and the number of unsaturation types per1000 carbons calculated by multiplying the different groups by 1000 anddividing the result by the total number of carbons. The number averagemolecular weight (Mn) was calculated by dividing the total number ofunsaturated species into 14,000, and has units of g/mol.

In one or more embodiments, the polyethylene compositions may includegreater than 0.10, in other embodiments greater than 0.18, and in otherembodiments greater than 0.20 total internal unsaturations (i.e.Vy1+Vy2+T1) per 1000 carbon atoms. In these or other embodiments, thepolyethylene compositions may include less than 0.40, in otherembodiments less than 0.30, in other embodiments less than 0.25 totalinternal unsaturations per 1000 carbon atoms. In one or moreembodiments, the polyethylene composition of the present invention mayinclude from about 0.10 to 0.40, in other embodiments from 0.18 to 0.30,and in other embodiments from 0.20 to 0.25 total internal unsaturationsper 1000 carbon atoms.

In one or more embodiments, the polyethylene compositions may includegreater than 0.08, in other embodiments greater than 0.12, and in otherembodiments greater than 0.15 tri-substituted olefins (i.e. T1) per 1000carbon atoms. In these or other embodiments, the polyethylenecompositions may include less than 0.35, in other embodiments less than0.25, in other embodiments less than 0.23 tri-substituted olefins per1000 carbon atoms. In one or more embodiments, the polyethylenecomposition of the present invention may include from about 0.08 to0.35, in other embodiments from 0.12 to 0.25, and in other embodimentsfrom 0.15 to 0.23 tri-substituted olefins per 1000 carbon atoms.

In one or more embodiments, the polyethylene compositions may includegreater than 0.02, in other embodiments greater than 0.04, and in otherembodiments greater than 0.05 unsaturations without carbon substitution(i.e. Vy1+Vy2) per 1000 carbon atoms. In these or other embodiments, thepolyethylene compositions may include less than 0.10, in otherembodiments less than 0.08, in other embodiments less than 0.06unsaturations without carbon substitution per 1000 carbon atoms. In oneor more embodiments, the polyethylene composition of the presentinvention may include from about 0.02 to 0.10, in other embodiments from0.04 to 0.08, and in other embodiments from 0.05 to 0.06 unsaturationswithout carbon substitution per 1000 carbon atoms.

Density

The polyethylene compositions of the present invention may becharacterized by their density, which is determined according to ASTM D1505 using a density-gradient column on a samples molded according toASTM D 4703-10a, Procedure C, and then conditioned under ASTM D 618-08(23°±2° C. and 50±10% relative humidity) for 40 hours prior to testing.According to embodiments of the present invention, the polyethylenecompositions may have a density of greater than 0.890, in otherembodiments greater than 0.900, and in other embodiments greater than0.914 g/ml. In these or other embodiments, the polyethylene compositionsmay have a density of less than 0.940, in other embodiments less than0.930, and in other embodiments less than 0.925 g/ml. In particularembodiments, the polyethylene compositions have a density from 0.890 to0.940, in other embodiments from 0.900 to 0.920, in other embodimentsfrom 0.912 to 0.917, in other embodiments from 0.918 to 0.928, and inother embodiments from 0.914 to 0.917.

Melt Index

The polyethylene compositions of the present invention may becharacterized by their melt index (MI), which may also be referred to asI2, reported in g/10 min, as determined according to ASTM D1238, 190°C., 2.16 kg load. According to embodiments of the present invention, thepolyethylene compositions may have a MI of greater than 0.1, in otherembodiments greater than 0.3, and in other embodiments greater than 0.5g/10 min. In these or other embodiments, the polyethylene compositionsmay have a MI of less than 6.0, in other embodiments less than 5.0, andin other embodiments less than 4.0 g/10 min. In one or more embodiments,the polyethylene compositions have a MI of from about 0.1 to about 6.0,in other embodiments from about 0.3 to about 5.0, and in otherembodiments from about 0.5 to about 4.0 g/10 min.

The polyethylene compositions of the present invention may becharacterized by their high load melt index (HLMI), which may also bereferred to as 121, reported in g/10 min, as determined according toASTM D1238, 190° C., 21.6 kg load. According to embodiments of thepresent invention, the polyethylene compositions may have a HLMI ofgreater than 5.0, in other embodiments greater than 7.0, and in otherembodiments greater than 10 g/10 min. In these or other embodiments, thepolyethylene compositions may have a HLMI of less than 40, in otherembodiments less than 35, and in other embodiments less than 30 g/10min. In one or more embodiments, the polyethylene compositions have aHLMI of from about 5.0 to about 40, in other embodiments from about 7.0to about 35, and in other embodiments from about 10 to about 30 g/10min.

The polyethylene compositions of the present invention may becharacterized by their Melt index ratio (MIR) or HLMI/MI ratio, which isHLMI divided by MI, both of which are determined by ASTM D1238.According to embodiments of the present invention, the polyethylenecompositions may have a MIR of greater than 20, in other embodimentsgreater than 23, and in other embodiments greater than 25. In these orother embodiments, the polyethylene compositions may have a MIR of lessthan 40, in other embodiments less than 37, and in other embodimentsless than 35. In one or more embodiments, the polyethylene compositionshave a MIR of from about 20 to about 40, in other embodiments from about23 to about 37, and in other embodiments from about 25 to about 35.

GPC 4D Methodology

Unless otherwise indicated, the distribution and the moments ofmolecular weight (Mw, Mn, Mz, Mw/Mn, etc.), the comonomer content (C2,C3, C6, etc.), and the branching index (g′) are determined by using ahigh temperature Gel Permeation Chromatography (Polymer Char GPC-IR)equipped with a multiple-channel band-filter based Infrared detectorIR5, an 18-angle light scattering detector and a viscometer. ThreeAgilent PLgel 10-μm Mixed-B LS columns are used to provide polymerseparation. Aldrich reagent grade 1,2,4-trichlorobenzene (TCB) with 300ppm antioxidant butylated hydroxytoluene (BHT) is used as the mobilephase. The TCB mixture is filtered through a 0.1-μm Teflon filter anddegassed with an online degasser before entering the GPC instrument. Thenominal flow rate is 1.0 ml/min and the nominal injection volume is 200μL. The whole system including transfer lines, columns, and detectorsare contained in an oven maintained at 145° C. Given amount of polymersample is weighed and sealed in a standard vial with 80-4 flow marker(Heptane) added to it. After loading the vial in the autosampler,polymer is automatically dissolved in the instrument with 8 ml added TCBsolvent. The polymer is dissolved at 160° C. with continuous shaking forabout 1 hour for most polyethylene samples or 2 hours for polypropylenesamples. The TCB densities used in concentration calculation are 1.463g/ml at room temperature and 1.284 g/ml at 145° C. The sample solutionconcentration is from 0.2 to 2.0 mg/ml, with lower concentrations beingused for higher molecular weight samples. The concentration (c), at eachpoint in the chromatogram is calculated from the baseline-subtracted IRSbroadband signal intensity (I), using the following equation: c=βI,where β is the mass constant. The mass recovery is calculated from theratio of the integrated area of the concentration chromatography overelution volume and the injection mass which is equal to thepre-determined concentration multiplied by injection loop volume. Theconventional molecular weight (IR MW) is determined by combininguniversal calibration relationship with the column calibration which isperformed with a series of monodispersed polystyrene (PS) standardsranging from 700 to 10M gm/mole. The MW at each elution volume iscalculated with following equation:

${{\log M} = {\frac{\log\left( {K_{PS}/K} \right)}{\alpha + 1} + {\frac{\alpha_{PS} + 1}{\alpha + 1}\log M_{PS}}}},$where the variables with subscript “PS” stand for polystyrene whilethose without a subscript are for the test samples. In this method,α_(PS)=0.67 and K_(PS)=0.000175, while a and K for other materials areas calculated and published in literature (Sun, T. et al. Macromolecules2001, 34, 6812), except that for purposes of this invention and claimsthereto, α=0.695 and K=0.000579 for linear ethylene polymers, α=0.705and K=0.0002288 for linear propylene polymers, α=0.695 and K=0.000181for linear butene polymers, α is 0.695 and K is0.000579*(1−0.0087*w2b+0.000018*(w2b){circumflex over ( )}2) forethylene-butene copolymer where w2b is a bulk weight percent of butenecomonomer, α is 0.695 and K is 0.000579*(1−0.0075*w2b) forethylene-hexene copolymer where w2b is a bulk weight percent of hexenecomonomer, and α is 0.695 and K is 0.000579*(1-0.0077*w2b) forethylene-octene copolymer where w2b is a bulk weight percent of octenecomonomer. Concentrations are expressed in g/cm³, molecular weight isexpressed in g/mole, and intrinsic viscosity (hence K in theMark-Houwink equation) is expressed in dL/g unless otherwise noted.

The comonomer composition is determined by the ratio of the IRS detectorintensity corresponding to CH₂ and CH₃ channel calibrated with a seriesof PE and PP homo/copolymer standards whose nominal value arepredetermined by NMR or FTIR. In particular, this provides the methylsper 1000 total carbons (CH₃/1000TC) as a function of molecular weight.The short-chain branch (SCB) content per 1000TC (SCB/1000TC) is thencomputed as a function of molecular weight by applying a chain-endcorrection to the CH₃/1000TC function, assuming each chain to be linearand terminated by a methyl group at each end. The weight % comonomer isthen obtained from the following expression in which f is 0.3, 0.4, 0.6,0.8, and so on for C3, C4, C6, C8, and so on co-monomers, respectively:w2=f*SCB/1000 TC.

The bulk composition of the polymer from the GPC-IR and GPC-4D analysesis obtained by considering the entire signals of the CH₃ and CH₂channels between the integration limits of the concentrationchromatogram. First, the following ratio is obtained

${{Bulk}\mspace{14mu}{IR}\mspace{14mu}{ratio}} = {\frac{{Area}\mspace{14mu}{of}\mspace{14mu}{CH}_{3}\mspace{14mu}{signal}\mspace{14mu}{within}\mspace{14mu}{integration}\mspace{14mu}{limits}}{{Area}\mspace{14mu}{of}\mspace{14mu}{CH}_{2}\mspace{14mu}{signal}\mspace{14mu}{within}\mspace{14mu}{integration}\mspace{14mu}{limits}}.}$

Then the same calibration of the CH₃ and CH₂ signal ratio, as mentionedpreviously in obtaining the CH3/1000TC as a function of molecularweight, is applied to obtain the bulk CH3/1000TC. A bulk methyl chainends per 1000TC (bulk CH3end/1000TC) is obtained by weight-averaging thechain-end correction over the molecular-weight range.

Thenw2b=f*bulk CH3/1000 TCbulk SCB/1000 TC=bulk CH3/1000 TC−bulk CH3end/1000 TC,and bulk SCB/1000TC is converted to bulk w2 in the same manner asdescribed above.

The LS detector is the 18-angle Wyatt Technology High Temperature DAWNHELEOSII. The LS molecular weight (M) at each point in the chromatogramis determined by analyzing the LS output using the Zimm model for staticlight scattering (Light Scattering from Polymer Solutions; Huglin, M.B., Ed.; Academic Press, 1972.):

${\frac{K_{o}c}{\Delta{R(\theta)}} = {\frac{1}{{MP}(\theta)} + {2A_{2}c}}}.$

Here, ΔR(θ) is the measured excess Rayleigh scattering intensity atscattering angle θ, c is the polymer concentration determined from theIR5 analysis, A₂ is the second virial coefficient, P(θ) is the formfactor for a monodisperse random coil, and K_(o) is the optical constantfor the system:

${K_{o} = \frac{4\pi^{2}{n^{2}\left( {d{n/d}c} \right)}^{2}}{\lambda^{4}N_{A}}},$where N_(A) is Avogadro's number, and (dn/dc) is the refractive indexincrement for the system. The refractive index, n=1.500 for TCB at 145°C. and λ=665 nm. For analyzing polyethylene homopolymers,ethylene-hexene copolymers, and ethylene-octene copolymers, dn/dc=0.1048ml/mg and A₂=0.0015; for analyzing ethylene-butene copolymers,dn/dc=0.1048*(1−0.00126*w2) ml/mg and A₂=0.0015 where w2 is weightpercent butene comonomer.

A high temperature Agilent (or Viscotek Corporation) viscometer, whichhas four capillaries arranged in a Wheatstone bridge configuration withtwo pressure transducers, is used to determine specific viscosity. Onetransducer measures the total pressure drop across the detector, and theother, positioned between the two sides of the bridge, measures adifferential pressure. The specific viscosity, η_(S), for the solutionflowing through the viscometer is calculated from their outputs. Theintrinsic viscosity, [η], at each point in the chromatogram iscalculated from the equation [η]=η_(S)/c, where c is concentration andis determined from the IRS broadband channel output. The viscosity MW ateach point is calculated as M=K_(PS)M^(α) ^(PS) ⁺¹/[η], where α_(PS) is0.67 and K_(PS) is 0.000175.

The branching index (g′_(vis)) is calculated using the output of theGPC-IRS-LS-VIS method as follows. The average intrinsic viscosity,[η]_(avg), of the sample is calculated by:

${\lbrack\eta\rbrack_{avg} = \frac{\sum{c_{i}\lbrack\eta\rbrack}_{i}}{\sum c_{i}}},$where the summations are over the chromatographic slices, i, between theintegration limits.

The branching index g′_(vis) is defined as

${g_{vis}^{\prime} = \frac{\lbrack\eta\rbrack_{avg}}{KM_{v}^{\alpha}}},$where M_(V) is the viscosity-average molecular weight based on molecularweights determined by LS analysis and the K and α are for the referencelinear polymer, which are, for purposes of this invention and claimsthereto, α=0.695 and K=0.000579 for linear ethylene polymers, α=0.705and K=0.0002288 for linear propylene polymers, α=0.695 and K=0.000181for linear butene polymers, α is 0.695 and K is0.000579*(1−0.0087*w2b+0.000018*(w2b){circumflex over ( )}2) forethylene-butene copolymer where w2b is a bulk weight percent of butenecomonomer, α is 0.695 and K is 0.000579*(1−0.0075*w2b) forethylene-hexene copolymer where w2b is a bulk weight percent of hexenecomonomer, and α is 0.695 and K is 0.000579*(1−0.0077*w2b) forethylene-octene copolymer where w2b is a bulk weight percent of octenecomonomer. Concentrations are expressed in g/cm³, molecular weight isexpressed in g/mole, and intrinsic viscosity (hence K in theMark-Houwink equation) is expressed in dL/g unless otherwise noted.Calculation of the w2b values is as discussed above.

The reversed-co-monomer index (RCI,m) is computed from x2 (mol %co-monomer C3, C4, C6, C8, etc.), as a function of molecular weight,where x2 is obtained from the following expression in which n is thenumber of carbon atoms in the comonomer (3 for C3, 4 for C4, 6 for C6,etc.):

${{x2} = {- \frac{200w2}{{{- 1}00n} - {2w2} + {nw2}}}}.$

Then the molecular-weight distribution, W(z) where z=log₁₀ M, ismodified to W′(z) by setting to 0 the points in W that are less than 5%of the maximum of W; this is to effectively remove points for which theS/N in the composition signal is low. Also, points of W′ for molecularweights below 2000 gm/mole are set to 0. Then W′ is renormalized so that1=∫_(−∞) ^(∞) W′dzand a modified weight-average molecular weight (M_(w)′) is calculatedover the effectively reduced range of molecular weights as follows:M _(w)′=∫_(−∞) ^(∞)10^(z) *W′dz.

The RCI,m is then computed asRCI,m=∫ _(−∞) ^(∞)×2(10^(z) −M _(w)′)W′dz.

A reversed-co-monomer index (RCI,w) is also defined on the basis of theweight fraction co-monomer signal (w2/100) and is computed as follows:

${RCI},{w = {\int_{- \infty}^{\infty}{\frac{w2}{100}\left( {{10^{Z}} - M_{w}^{\prime}} \right)W^{\prime}{{dz}.}}}}$

Note that in the above definite integrals the limits of integration arethe widest possible for the sake of generality; however, in reality thefunction is only integrated over a finite range for which data isacquired, considering the function in the rest of the non-acquired rangeto be 0. Also, by the manner in which W′ is obtained, it is possiblethat W′ is a discontinuous function, and the above integrations need tobe done piecewise.

Three co-monomer distribution ratios are also defined on the basis ofthe % weight (w2) comonomer signal, denoted as CDR-1,w, CDR-2,w, andCDR-3,w, as follows:

${{CDR}\text{-}1},{w = \frac{w2({Mz})}{w2\left( {Mw} \right)}},{{CDR}\text{-}2},{w = \frac{w2({Mz})}{w2\left( \frac{{Mw} + {Mn}}{2} \right)}},{{{CDR}\text{-}3} = \frac{w2\left( \frac{{Mz} + {Mw}}{2} \right)}{w2\left( \frac{{Mw} + {Mn}}{2} \right)}},$where w2(Mw) is the % weight co-monomer signal corresponding to amolecular weight of Mw, w2(Mz) is the % weight co-monomer signalcorresponding to a molecular weight of Mz, w2[(Mw+Mn)/2)] is the %weight co-monomer signal corresponding to a molecular weight of(Mw+Mn)/2, and w2[(Mz+Mw)/2] is the % weight co-monomer signalcorresponding to a molecular weight of Mz+Mw/2, where Mw is theweight-average molecular weight, Mn is the number-average molecularweight, and Mz is the z-average molecular weight.

Accordingly, the co-monomer distribution ratios can be also definedutilizing the % mole co-monomer signal, CDR-1,m, CDR-2,m, CDR-3,m, as

${{CDR}\text{-}1},{m = \frac{x\; 2({Mz})}{x\; 2\left( {Mw} \right)}},{{CDR}\text{-}2},{m = \frac{x\; 2({Mz})}{x\; 2\left( \frac{{Mw} + {Mn}}{2} \right)}},{{{CDR}\text{-}3} = \frac{x\; 2\left( \frac{{Mz} + {Mw}}{2} \right)}{x\; 2\left( \frac{{Mw} + {Mn}}{2} \right)}},$where x2(Mw) is the % mole co-monomer signal corresponding to amolecular weight of Mw, x2(Mz) is the % mole co-monomer signalcorresponding to a molecular weight of Mz, x2[(Mw+Mn)/2)] is the % moleco-monomer signal corresponding to a molecular weight of (Mw+Mn)/2, andx2[(Mz+Mw)/2] is the % mole co-monomer signal corresponding to amolecular weight of Mz+Mw/2, where Mw is the weight-average molecularweight, Mn is the number-average molecular weight, and Mz is thez-average molecular weight.

All molecular weights are weight average (Mw) unless otherwise noted.All molecular weights are reported in g/mol unless otherwise noted.

Molecular Weight

The polyethylene compositions of the present invention may becharacterized by their number average molecular weight (Mn), which maybe measured by using the technique set forth above. According toembodiments of the present invention, the polyethylene compositions mayhave a Mn of greater than 10,000, in other embodiments greater than12,000, and in other embodiments greater than 15,000 g/mol. In these orother embodiments, the polyethylene compositions may have a Mn of lessthan 100,000, in other embodiments less than 80,000, and in otherembodiments less than 60,000 g/mol. In one or more embodiments, thepolyethylene compositions have a Mn of from about 10,000 to about100,000, in other embodiments from about 12,000 to about 80,000, and inother embodiments from about 15,000 to about 60,000 g/mol.

The polyethylene compositions of the present invention may becharacterized by their number average molecular weight (Mw), which maybe measured by using the technique set forth above. According toembodiments of the present invention, the polyethylene compositions mayhave a Mw of greater than 80,000, in other embodiments greater than90,000, and in other embodiments greater than 100,000 g/mol. In these orother embodiments, the polyethylene compositions may have a Mw of lessthan 250,000, in other embodiments less than 200,000, and in otherembodiments less than 180,000 g/mol. In one or more embodiments, thepolyethylene compositions have a Mw of from about 80,000 to about250,000, in other embodiments from about 90,000 to about 200,000, and inother embodiments from about 100,000 to about 180,000 g/mol.

The polyethylene compositions of the present invention may becharacterized by their z-average molecular weight (Mz), which may bemeasured by using the technique set forth above. According toembodiments of the present invention, the polyethylene compositions mayhave an Mz of greater than 210,000, in other embodiments greater than250,000, and in other embodiments greater than 275,000 g/mol. In theseor other embodiments, the polyethylene compositions may have an Mz ofless than 500,000, in other embodiments less than 450,000, and in otherembodiments less than 400,000 g/mol. In one or more embodiments, thepolyethylene compositions have an Mz of from about 210,000 to about500,000, in other embodiments from about 250,000 to about 450,000, andin other embodiments from about 275,000 to about 400,000 g/mol.

The polyethylene compositions of the present invention may becharacterized by their molecular weight distribution (Mw/Mn), which mayalso be referred to as polydispersity, where Mw and Mn may be measuredby using the technique set forth above. According to embodiments of thepresent invention, the polyethylene compositions may have an Mw/Mn ofgreater than 4.5, in other embodiments greater than 4.7, and in otherembodiments greater than 4.9. In these or other embodiments, thepolyethylene compositions may have an Mw/Mn of less than 12, in otherembodiments less than 11, and in other embodiments less than 9.5. In oneor more embodiments, the polyethylene compositions have an Mw/Mn of fromabout 4.5 to about 12, in other embodiments from about 4.7 to about 12,and in other embodiments from about 4.9 to about 9.5.

The polyethylene compositions of the present invention may becharacterized by their ratio of z-average molecular weight to weightaverage molecular weight (Mz/Mw), where Mz and Mw may be measured byusing the technique set forth above. According to embodiments of thepresent invention, the polyethylene compositions may have an Mz/Mw ofgreater than 2.0, in other embodiments greater than 2.2, and in otherembodiments greater than 2.3. In these or other embodiments, thepolyethylene compositions may have an Mz/Mw of less than 3.0, in otherembodiments less than 2.9, and in other embodiments less than 2.8. Inone or more embodiments, the polyethylene compositions have an Mz/Mw offrom about 2.0 to about 3.0, in other embodiments from about 2.2 toabout 2.9, and in other embodiments from about 2.3 to about 2.8.

The polyethylene compositions of the present invention may becharacterized by their ratio of z-average molecular weight to numberaverage molecular weight (Mz/Mn), where Mz and Mn may be measured byusing the technique set forth above. According to embodiments of thepresent invention, the polyethylene compositions may have an Mz/Mn ofgreater than 7.0, in other embodiments greater than 10, and in otherembodiments greater than 11. In these or other embodiments, thepolyethylene compositions may have an Mz/Mn of less than 20, in otherembodiments less than 18, and in other embodiments less than 17. In oneor more embodiments, the polyethylene compositions have an Mz/Mw of fromabout 7.0 to about 20, in other embodiments from about 10 to about 18,and in other embodiments from about 11 to about 17.

Branching Index

The polyethylene compositions of the present invention may becharacterized by their branching index g′_((vis)), which may becalculated by using the technique set forth above. Generally, thepolyethylene composition of the present invention are substantially freeof long-chain branching, which polymer compositions are characterized bya g′_((vis)) proximate to 1.0. According to embodiments of the presentinvention, the polyethylene compositions of the invention may have ag′_((vis)) of greater than 0.90, in other embodiments greater than 0.92,in other embodiments greater than 0.94, and in other embodiments greaterthan 0.96.

Reversed-Co-Monomer Index

The polyethylene compositions of the present invention may becharacterized by their reversed-co-monomer index (RCI,m), which may becalculated by using the technique set forth above. According toembodiments of the present invention, the polyethylene compositions mayhave a RCI,m of greater than 35, in other embodiments greater than 55,and in other embodiments greater than 70 kg/mol. In these or otherembodiments, the polyethylene compositions may have a RCI,m of less than190, in other embodiments less than 160, and in other embodiments lessthan 140 kg/mol. In one or more embodiments, the polyethylenecompositions have a RCI,m of from about 35 to about 190, in otherembodiments from about 55 to about 165, and in other embodiments fromabout 70 to about 140 kg/mol.

Comonomer Distribution Ratio

The polyethylene compositions of the present invention may becharacterized by their comonomer distribution ratio-2 (CDR-2,m), whichmay be calculated by using the technique set forth above. According toembodiments of the present invention, the polyethylene compositions mayhave a CDR-2,m of greater than 1.20, in other embodiments greater than1.30, and in other embodiments greater than 1.40. In these or otherembodiments, the polyethylene compositions may have a CDR-2,m of lessthan 1.80, in other embodiments less than 1.70, and in other embodimentsless than 1.60. In one or more embodiments, the polyethylenecompositions have a CDR-2,m of from about 1.20 to about 1.80, in otherembodiments from about 1.30 to about 1.70, and in other embodiments fromabout 1.40 to about 1.60.

Temperature Rising Elution Fractionation (TREF)

Temperature Rising Elution Fractionation (TREF) analysis is done using aCRYSTAF-TREF 200+ instrument from Polymer Char, S. A., Valencia, Spain.The principles of TREF analysis and a general description of theparticular apparatus to be used are given in the article Monrabal, B.;del Hierro, P. Anal. Bioanal. Chem. 2011, 399, 1557. FIG. 3 of thearticle is an appropriate schematic of the particular apparatus used;however, the connections to the 6-port valve shown in FIG. 3 differ fromthe apparatus to be used in that the tubing connected to the 11-o'clockport is connected to the 9-o'clock port and the tubing connected to the9-o'clock port is connected to the 11-o'clock port. Pertinent details ofthe analysis method and features of the apparatus to be used are asfollows.

1,2-Dichlorobenzene (ODCB) solvent stabilized with approximately 380 ppmof 2,6-bis(1,1-dimethylethyl)-4-methylphenol (butylated hydroxytoluene)is used for preparing the sample solution and for elution. The sample tobe analyzed (approximately 25 mg but as low as approximately 10 mg) isdissolved in ODCB (25 ml metered at ambient temperature) by stirring at150° C. for 60 min. A small volume (0.5 ml) of the solution isintroduced into a column (15-cm long by ⅜″ o.d.) packed with an inertsupport (of stainless steel balls) at 150° C., and the columntemperature is stabilized at 140° C. for 45 min. The sample volume isthen allowed to crystallize in the column by reducing the temperature to30° C. at a cooling rate of 1° C./min. The column is kept at 30° C. for15 min before injecting the ODCB flow (1 ml/min) into the column for 10min to elute and measure the polymer that did not crystallize (solublefraction). The infrared detector used (Polymer Char IR4) generates anabsorbance signal that is proportional to the concentration of polymerin the eluting flow. A complete TREF curve is then generated byincreasing the temperature of the column from 30° C. to 140° C. at arate of 2° C./min while maintaining the ODCB flow at 1 ml/min to eluteand measure the dissolving polymer.

The polyethylene compositions of the present invention have two peaks inthe TREF measurement, which is described below. Two peaks in the TREFmeasurement as used in this specification and the appended claims meansthe presence of two distinct normalized ELS (evaporation mass lightscattering) response peaks in a graph of normalized ELS response(vertical or y axis) versus elution temperature (horizontal or x axiswith temperature increasing from left to right) using the TREF methodbelow. A “peak” in this context means where the general slope of thegraph changes from positive to negative with increasing temperature.Between the two peaks is a local minimum in which the general slope ofthe graph changes from negative to positive with increasing temperature.“General trend” of the graph is intended to exclude the multiple localminimums and maximums that can occur in intervals of 2° C. or less. Inother embodiments, the two distinct peaks are at least 3° C. apart, inother embodiments at least 4° C. apart, and in other embodiments atleast 5° C. apart. Additionally, both of the distinct peaks occur at atemperature on the graph above 20° C. and below 120° C. where theelution temperature is run to 0° C. or lower. This limitation avoidsconfusion with the apparent peak on the graph at low temperature causedby material that remains soluble at the lowest elution temperature. Twopeaks on such a graph indicates a bi-modal composition distribution(CD). Bimodal CD may also be determined by other methods known to thoseskilled in the art. One such alternate method for TREF measurement thencan be used if the above method does not show two peaks is disclosed inB. Monrabal, “Crystallization Analysis Fractionation: A New Techniquefor the Analysis of Branching Distribution in Polyolefins,” Journal ofApplied Polymer Science, Vol. 52, 491-499 (1994).

The T₇₅-T₂₅ value represents the homogeneity of the compositiondistribution as determined by temperature rising elution fractionation.A TREF curve is produced as described below. Then the temperature atwhich 75% of the polymer is eluted is subtracted from the temperature atwhich 25% of the polymer is eluted, as determined by the integration ofthe area under the TREF curve. The T₇₅-T₂₅ value represents thedifference. The closer these temperatures comes together, the narrowerthe composition distribution.

Composition Distribution Breadth (T₇₅-T₂₅)

The polyethylene compositions of one or more embodiments of the presentinvention are characterized by a composition distribution breadthT₇₅-T₂₅, as measured by TREF, of greater than 10° C., in otherembodiments greater than 15° C., and in other embodiments greater than18° C. In these or other embodiments, the polyethylene compositions ofthe present invention are characterized by a composition distributionbreadth T₇₅-T₂₅, as measured by TREF, of less than 35° C., in otherembodiments less than 27° C., and in other embodiments less than 22° C.In one or more embodiments, particularly those polyethylene compositionshaving a density of 0.912 to 0.917, the polyethylene compositions ofthis invention have a composition distribution breadth T₇₅-T₂₅, asmeasured by TREF, of from about 10 to about 35° C., in other embodimentsfrom about 15 to about 27° C., and in other embodiments from about 18 toabout 22° C.

Cross-Fractionation Chromatography (CFC)

Cross-fractionation chromatography (CFC) analysis is done using a CFC-2instrument from Polymer Char, S.A., Valencia, Spain. The principles ofCFC analysis and a general description of the particular apparatus usedare given in the article by Ortin, A.; Monrabal, B.; Sancho-Tello, 257J. MACROMOL. SYMP. 13 (2007). In FIG. 1 of the article is an appropriateschematic of the particular apparatus used. Pertinent details of theanalysis method and features of the apparatus used are as follows.

The solvent used for preparing the sample solution and for elution was1,2-Dichlorobenzene (ODCB) which was stabilized by dissolving 2 g of2,6-bis(1,1-dimethylethyl)-4-methylphenol (butylated hydroxytoluene) ina 4-L bottle of fresh solvent at ambient temperature. The sample to beanalyzed (25-125 mg) was dissolved in the solvent (25 ml metered atambient temperature) by stirring (200 rpm) at 150° C. for 75 min. Asmall volume (0.5 ml) of the solution was introduced into a TREF column(stainless steel; o.d., ⅜″; length, 15 cm; packing, non-porous stainlesssteel micro-balls) at 150° C., and the column temperature was stabilizedfor 30 min at a temperature (120-125° C.) approximately 20° C. higherthan the highest-temperature fraction for which the GPC analysis wasincluded in obtaining the final bivariate distribution. The samplevolume was then allowed to crystallize in the column by reducing thetemperature to an appropriate low temperature (30, 0, or −15° C.) at acooling rate of 0.2° C./min. The low temperature was held for 10 minbefore injecting the solvent flow (1 ml/min) into the TREF column toelute the soluble fraction (SF) into the GPC columns (3×PLgel 10 μmMixed-B 300×7.5 mm, Agilent Technologies, Inc.); the GPC oven was heldat high temperature (140° C.). The SF was eluted for 5 min from the TREFcolumn and then the injection valve was put in the “load” position for40 min to completely elute all of the SF through the GPC columns(standard GPC injections). All subsequent higher-temperature fractionswere analyzed using overlapped GPC injections wherein at eachtemperature step the polymer was allowed to dissolve for at least 16 minand then eluted from the TREF column into the GPC column for 3 min. TheIR4 (Polymer Char) infrared detector was used to generate an absorbancesignal that is proportional to the concentration of polymer in theeluting flow.

The universal calibration method was used for determining the molecularweight distribution (MWD) and molecular-weight averages (Mn, Mw, etc.)of eluting polymer fractions. Thirteen narrow molecular-weightdistribution polystyrene standards (obtained from Agilent Technologies,Inc.) within the range of 1.5-8200 kg/mol were used to generate auniversal calibration curve. Mark-Houwink parameters were obtained fromAppendix I of Mori, S.; Barth, H. G. Size Exclusion Chromatography;Springer, 1999. For polystyrene K=1.38×10⁻⁴ dl/g and α=0.7; and forpolyethylene K=5.05×10⁴ dl/g and α=0.693 were used. For a polymerfraction, which eluted at a temperature step, that has a weight fraction(weight % recovery) of less than 0.5%, the MWD and the molecular-weightaverages were not computed; additionally, such polymer fractions werenot included in computing the MWD and the molecular-weight averages ofaggregates of fractions.

Measuring Tw₁, Tw₂, Mw₁ and Mw₂ from CFC

The techniques and calculations to determine Tw₁, Tw₂, Mw₁, and Mw₂ fromCFC data are described in U.S. Publication No. 2016/0347888, which isincorporated herein by reference. CFC data reported from the instrumentsoftware CFC-2 instrument) includes “Fraction Summary” where eachfraction is listed by its fractionation temperature (Ti), thecorresponding normalized weight % value (Wi), the cumulative weight %,and various moments of molecular weight averages (including weightaverage molecular weight, Mwi). From this data, the temperature at which100% of the material has eluted, as well as the closest point at which50% of the polymer has eluted, is determined by the integral, which isused then to divide the fractionations into a 1^(st)-half and a2^(nd)-half.

For example, and with reference to FIGS. 1A and 1B, the x-axisrepresents the elution temperature in centigrade, while the right handy-axis represents the value of the integral of the weights of polymerthat have been eluted up to an elution temperature. The temperature atwhich 100% of the material has eluted in this example is about 100° C.,and the closest point at which 50% of the polymer has eluted is 84° C.Accordingly, the first fraction Ti is less than or equal to 84° C. andthe second fraction is greater than 84° C. Fractions without molecularweight averages are excluded, which in this example includes thosefractions with Ti between 25 and 40° C.

Once the data is divided into two roughly equal halves, weight averagesof Ti and Mwi for each half (i.e. Tw₁, Tw₂, Mw₁ and Mw₂) are calculatedaccording to the conventional definition of weight average. Namely, Tiand Mwi are used to calculate the weight average elution temperature foreach half using the formula shown in Eqn. 1.

$\begin{matrix}{{{Tw} = \frac{\Sigma\;{TiWi}}{\Sigma\;{Wi}}},} & {{Eqn}.\mspace{14mu} 1}\end{matrix}$where Ti represents the elution temperature for each eluted fraction,and Wi represents the normalized weight % (polymer amount) of eacheluted fraction. Fractions that did not have sufficient quantity (i.e.,<0.5 wt. %) to be processed for molecular weight averages in theoriginal data file are excluded from the calculation of Tw₁, Tw₂, Mw₁and Mw₂.

With reference again to FIG. 1A, the weight average elution temperatureis 64.9° C. for the first half and 91.7° C. for the second half.

Similarly, the weight average molecular weight (Mwi) of each elutedfraction is used to calculate the weight average molecular weight foreach half using the formula shown in Eqn. 2.

$\begin{matrix}{{{Mw} = \frac{\Sigma\;{MwiWi}}{\Sigma\;{Wi}}},} & {{Eqn}.\mspace{14mu} 2}\end{matrix}$where Mw represents the weight average molecular weight of each elutedfraction, and Wi represents the normalized weight % (polymer amount) ofeach eluted fraction.

With reference again to FIG. 1B, the weight average molecular weight is237,539 g/mol for the first half and 74,156 g/mol for the second half.

The values calculated using the techniques described above may be usedto classify the MWD×SCBD for experimental polymers and control polymers.

Ratio of Molecular Weight of TREF Elution Fractions (Mw₁/Mw₂)

The polyethylene compositions of the present invention may becharacterized by their ratio of a weight average molecular weight for afirst half or fraction (Mw1) of a temperature rising elution (TREF)curve from cross-fractionation (CFC) to a weight average molecularweight for a second half or fraction (Mw₂) of the TREF curve, where Mw₁and Mw₂ may be calculated by using the technique set forth above.According to embodiments of the present invention, the polyethylenecompositions may be characterized by a ratio Mw₁/Mw₂ of greater than1.2, in other embodiments greater than 1.35, and in other embodimentsgreater than 1.5. In these or other embodiments, the polyethylenecompositions may be characterized by a ratio Mw₁/Mw₂ of less than 2.0,in other embodiments less than 1.85, and in other embodiments less than1.80. In one or more embodiments, the polyethylene compositions may becharacterized by a ratio Mw₁/Mw₂ of from about 1.2 to about 2.0, inother embodiments from about 1.35 to about 1.85, and in otherembodiments from about 1.50 to about 1.80.

Difference of Weight Average TREF Elution Temperatures (Tw₁-Tw₂)

The polyethylene compositions of the present invention may becharacterized by their difference of a weight average elutiontemperature for a first half or fraction (Tw₁) of a temperature risingelution (TREF) curve from cross-fractionation (CFC) to a weight averageelution temperature for a second half or fraction (Tw₂) of the TREFcurve, where Tw₁ and Tw₂ may be calculated by using the technique setforth above. According to embodiments of the present invention, thepolyethylene compositions may be characterized by a difference betweenthe first half weight average elution temperature and the second halfweight average elution temperature (Tw₁−Tw₂) of greater than −25° C., inother embodiments greater than −24° C., and in other embodiments greaterthan −23° C. In these or other embodiments, the polyethylenecompositions may be characterized by a Tw₁−Tw₂ of less than −20° C., inother embodiments less than −20.5° C., and in other embodiments lessthan −21° C. In one or more embodiments, the polyethylene compositionsmay be characterized by a Tw₁−Tw₂ of from about −25.0 to about −20.0°C., in other embodiments from about −24.0 to about −20.5° C., and inother embodiments from about −23.0 to about −21.0° C.

Physical Characteristics of Films

Finished films (e.g. blown films) prepared from the polyethylenecompositions of the present invention may be characterized by their 1%Secant modulus, which may be determined according to ASTM D 882 byemploying a 15 mm width strip of material. According to embodiments ofthe present invention, films prepared from polyethylene compositionswith a density of 0.914 to 0.917 g/ml may have a 1% Secant modulus, inthe transverse direction, of greater than 30,000, in other embodimentsgreater than 32,000, and in other embodiments greater than 35,000 psi.

According to other embodiments of the present invention, films preparedfrom polyethylene compositions with a density of 0.918 to 0.921 g/ml mayhave a 1% Secant modulus, in the transverse direction, of greater than42,000, in other embodiments greater than 45,000, and in otherembodiments greater than 47,000 psi.

Yield Strength

Finished films (e.g. blown films) prepared from the polyethylenecompositions of the present invention may be characterized by theiryield strength, which may be determined according to ASTM D 882 byemploying a 15 mm width strip of material. According to embodiments ofthe present invention, the polyethylene compositions may have a yieldstrength, in the transverse direction, of greater than 1400, in otherembodiments greater than 1500, and in other embodiments greater than1600 psi.

Tensile Strength

Finished films (e.g. blown films) prepared from the polyethylenecompositions of the present invention may be characterized by theirtensile strength, which may be determined according to ASTM D 882 byemploying a 15 mm width strip of material. According to embodiments ofthe present invention, the polyethylene compositions may have a tensilestrength, in the transverse direction, of greater than 6500, in otherembodiments greater than 7000, and in other embodiments greater than7200 psi.

Dart Drop

Finished films (e.g. blown films) prepared from the polyethylenecompositions of the present invention may be characterized by theirimpact resistance, which is determined according to Dart F50, or DartDrop Impact or Dart Impact (DI), which is reported in grams (g) and/orgrams per mil (g/mil), as specified by ASTM D-1709, method A, using adart with a phenolic composite head. According to embodiments of thepresent invention, the DI of blown polyethylene films of this inventionmay be greater than 300 g/mil, in other embodiments greater than 400g/mil, and in other embodiments greater than 500 g/mil.

Puncture

Finished films (e.g. blown films) prepared from the polyethylenecompositions of the present invention may be characterized by theirpuncture resistance, which is determined according to a modified ASTM D5748 test using two 0.25 mil HDPE slip sheets, and a United SFM-1testing machine operating at 10 in/min operating with a Btec probe B.According to embodiments of the present invention, the punctureresistance of polyethylene films of this invention may be greater than22, in other embodiments greater than 23, and in other embodimentsgreater than 24 in·lbs/mil

Haze

Finished films prepared from the polyethylene compositions of thepresent invention may be characterized by their haze, which isquantified in accordance with ASTM D 1003. According to embodiments ofthe present invention, the haze of the finished polyethylene films ofthis invention may be less than 30%, in other embodiments less than 20%,in other embodiments less than 15%, and in other embodiments less than13%. In one or more embodiments, the haze of the finished films may befrom about 3 to about 30, in other embodiments from about 5 to about 20,and in other embodiments from about 8 to about 15%.

Gloss

Finished films prepared from the polyethylene compositions of thepresent invention may be characterized by their gloss at 45°, which isdetermined in accordance with ASTM D 2457. According to embodiments ofthe present invention, the gloss at 45° of the finished polyethylenefilms of this invention may be greater than 6, in other embodimentsgreater than 8, and in other embodiments greater than 10. In these orother embodiments, the gloss at 45° of the finished films may be lessthan 22, in other embodiments less than 20, and in other embodimentsless than 18. In one or more embodiments, the gloss at 45° of thefinished films may be from about 6 to about 22, in other embodimentsfrom about 8 to about 20, and in other embodiments from about 10 toabout 18.

Tear

Finished films (e.g. blown films) prepared from the polyethylenecompositions of the present invention may be characterized by their tearresistance, which is determined according to Elmendorf Tear pursuant toASTM D 1922 with samples conditioned at 23°±2° C. and 50±10% relativehumidity for 40 hours prior to testing.

According to embodiments of the present invention, the tear resistanceof blown polyethylene films of this invention, in the machine direction,may be greater than 120 g/mil, in other embodiments greater than 130g/mil, and in other embodiments greater than 140 g/mil.

According to embodiments of the present invention, the tear resistanceof blown polyethylene films of this invention, in the transversedirection, may be greater than 550 g/mil, in other embodiments greaterthan 575 g/mil, and in other embodiments greater than 600 g/mil.

Production of Polyethylene Compositions

The polyethylene compositions of the present invention may be preparedby polymerizing olefin monomer by using a supported catalyst systemincluding: (i) a unbridged hafnium metallocene compound; (ii) anunbridged zirconium metallocene compound; (iii) a support material; and(iv) activator. In particular embodiments, the unbridged hafniummetallocene compound is represented by the formula (A):

where

M* is hafnium

each of R¹, R², R⁴ and R⁵ is independently hydrogen, alkoxide, or C₁ toC₄₀ substituted or unsubstituted hydrocarbyl;

R³ is —R¹¹—SiR′₃, where R¹¹ is a C1 to C4 hydrocarbyl, and each R′ isindependently hydrogen or a C₁ to C₂₀ substituted or unsubstitutedhydrocarbyl;

each R⁶, R⁷, R⁸, R⁹, and R¹⁰ is independently hydrogen, halide,alkoxide, C₁ to C₄₀ substituted or unsubstituted hydrocarbyl, or—R¹¹—SiR′₃, where R¹¹ is a C₁ to C₄ hydrocarbyl, and each R′ isindependently hydrogen or a C₁ to C₂₀ substituted or unsubstitutedhydrocarbyl; and

each X is independently a univalent anionic ligand, or two Xs are joinedto form a metallocyclic ring, or two Xs are joined to form a chelatingligand, a diene ligand, or an alkylidene ligand; and

the unbridged zirconium metallocene compound is represented formula (B):Cp_(m)MX_(q)  (B),wherein each Cp is, independently, a cyclopentadienyl group (such ascyclopentadiene, indene or fluorene) which may be substituted orunsubstituted, M is zirconium, X is a leaving group (such as a halide, ahydride, an alkyl group, an alkenyl group or an arylalkyl group), andm=2 or 3, q=0, 1, 2, or 3, and the sum of m+q is equal to the oxidationstate of the hafnium. In some embodiments, m=2 in the metallocenecatalyst compound.

As used herein, the term “metallocene compound” includes compoundshaving two or three Cp ligands (cyclopentadienyl and ligands isolobal tocyclopentadienyl) bound to at least one Zr or Hf metal atom, and one ormore leaving group(s) bound to the at least one metal atom.

For purposes of this specification in relation to all metallocenecatalyst compounds, the term “substituted” means that a hydrogen grouphas been replaced with a hydrocarbyl group, a heteroatom, or aheteroatom containing group. For example, methyl cyclopentadiene (Cp) isa Cp group substituted with a methyl group.

For purposes of this specification and claims thereto, “alkoxides”include those where the alkyl group is a C₁ to C₁₀ hydrocarbyl. Thealkyl group may be straight chain, branched, or cyclic. The alkyl groupmay be saturated or unsaturated. In some embodiments, the alkyl groupmay comprise at least one aromatic group.

Unbridged Hafnium Metallocene

In one or more embodiments, the unbridged hafnium metallocene compoundmay be represented by the formula (A):

where M* is hafnium; each of R¹, R², R⁴ and R⁵ is independentlyhydrogen, alkoxide, or C₁ to C₄₀ substituted or unsubstitutedhydrocarbyl; R³ is —R¹¹—SiR′3, where R¹¹ is a C₁ to C₄ hydrocarbyl, andeach R′ is independently hydrogen or a C₁ to C₂₀ substituted orunsubstituted hydrocarbyl; each R⁶, R⁷, R⁸, R⁹ and R¹⁰ is independentlyhydrogen, halide, alkoxide, C₁ to C₄₀ substituted or unsubstitutedhydrocarbyl, or —R¹¹—SiR′3, where R¹¹ is a C₁ to C₄ hydrocarbyl, andeach R′ is independently hydrogen or a C₁ to C₂₀ substituted orunsubstituted hydrocarbyl; and each X is independently a univalentanionic ligand, or two Xs are joined to form a metallocyclic ring, ortwo Xs are joined to form a chelating ligand, a diene ligand, or analkylidene ligand.

In particular embodiments, each R¹, R², R⁴ and R⁵ is independentlyhydrogen, or a substituted C₁ to C₂₀ hydrocarbyl group or anunsubstituted C₁ to C₂₀ hydrocarbyl group, and more particularly eachR¹, R², R⁴ and R⁵ is independently a C₁ to C₁₂ alkyl group; for example,each R¹, R², R⁴ and R⁵ is independently hydrogen, methyl, ethyl, propyl,butyl, pentyl, hexyl, or an isomer thereof, and in particularembodiments R¹, R², R⁴ and R⁵ is independently hydrogen or methyl.

In one or more embodiments, R³ is —R²⁰—SiR′3, where R²⁰ is a C₁ to C₄hydrocarbyl (e.g. CH₂; CH₂CH₂, (Me)CHCH₂, (Me)CH), and each R′ isindependently hydrogen or a C₁ to C₂₀ substituted or unsubstitutedhydrocarbyl (e.g. a substituted C₁ to C₁₂ hydrocarbyl group or anunsubstituted C₁ to C₁₂ hydrocarbyl group); for example, R′ is methyl,ethyl, propyl, butyl, pentyl, hexyl, phenyl, biphenyl, or an isomerthereof. In one or more embodiments, R′ is a C₁ to C₂₀ alkyl or aryl,such as methyl, methyl phenyl, phenyl, biphenyl, pentamethylphenyl,tetramethylphenyl, or di-t-butylphenyl. In one or more embodiments, atleast one R′ is not hydrogen, alternatively two of R′ are not hydrogen,alternatively three of R′ are not hydrogen.

Alternatively, R³ is —CH₂—SiMe₃, —CH₂—SiEt₃, —CH₂—SiPr₃, —CH₂—SiBu₃,—CH₂—SiCy₃, —CH₂—SiH(CH₃)₂, —CH₂SiPh₃, —CH₂—Si(CH₃)₂Ph, —CH₂—Si(CH₃)₂Ph,—CH₂—Si(CH₃)Ph₂, —CH₂—Si(Et)₂Ph, —CH₂—Si(Et)Ph₂, —CH₂—Si(CH₂)₃Ph,—CH₂—Si(CH₂)₄Ph, —CH₂—Si(Cy)Ph₂, or —CH₂—Si(Cy)₂Ph.

Alternatively, each of R¹, R², R³, and R⁴ is not hydrogen.

In one or more embodiments, each R⁶, R⁷, R⁸, and R¹⁰ is independentlyhydrogen, or a substituted C₁ to C₂₀ hydrocarbyl group or anunsubstituted C₁ to C₂₀ hydrocarbyl group, and more particularly eachR⁶, R⁷, R⁸ and R¹⁰ is independently a C₁ to C₁₂ alkyl group; forexample, each R⁶, R⁷, R⁸ and R¹⁰ is independently hydrogen, methyl,ethyl, propyl, butyl, pentyl, hexyl, or an isomer thereof, and inparticular embodiments R⁶, R⁷, R⁸ and R¹⁰ is independently hydrogen ormethyl.

In one or more embodiments, R⁹ is —R¹¹—SiR′₃, where R¹¹ is a C₁ to C₄hydrocarbyl, and each R′ is independently hydrogen or C₁ to C₂₀substituted or unsubstituted hydrocarbyl. In particular embodiments, R⁹is —R²⁰—SiR′₃, where R²⁰ is a C₁ to C₄ hydrocarbyl (e.g. CH₂; CH₂CH₂,(Me)CHCH₂, (Me)CH), and each R′ is independently hydrogen or a C₁ to C₂₀substituted or unsubstituted hydrocarbyl (e.g. a substituted C₁ to C₁₂hydrocarbyl group or an unsubstituted C₁ to C₁₂ hydrocarbyl group); forexample, R′ is methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl,biphenyl, or an isomer thereof. In one or more embodiments, R′ is a C₁to C₂₀ alkyl or aryl, such as methyl, methyl phenyl, phenyl, biphenyl,pentamethylphenyl, tetramethylphenyl, or di-t-butylphenyl. In one ormore embodiments, at least one R′ is not hydrogen, alternatively two ofR′ are not hydrogen, alternatively three of R′ are not hydrogen.

Alternatively, R⁹ is —CH₂—SiMe₃, —CH₂—SiEt₃, —CH₂—SiPr₃, —CH₂—SiBu₃,—CH₂—SiCy₃, —CH₂(C₆Me₅), —CH₂—C(CH₃)₂Ph, —CH₂—C(Cy)Ph₂. —CH₂—SiH(CH₃)₂,—CH₂SiPh₃, —CH₂—Si(CH₃)₂Ph, —CH₂—Si(CH₃)Ph₂, —CH₂—Si(Et)₂Ph,—CH₂—Si(Et)Ph₂, —CH₂—Si(CH₂)₃Ph, —CH₂—Si(CH₂)₄Ph, —CH₂—Si(Cy)Ph₂, or—CH₂—Si(Cy)₂Ph.

In one or more embodiments, R³ and R⁹ are both, independently,—R¹¹—SiR′₃, where R¹¹ is a C₁ to C₄ hydrocarbyl, and each R′ isindependently hydrogen or a C₁ to C₂₀ substituted or unsubstitutedhydrocarbyl. In particular embodiments, R³ and R⁹ are, independently,—R²⁰—SiR′₃, where R²⁰ is a C₁ to C₄ hydrocarbyl (such as —CH₂—,—CH₂CH₂—, —(Me)CHCH₂—, —(Me)CH—), and each R′ is independently hydrogen,or a C₁ to C₂₀ substituted or unsubstituted hydrocarbyl (e.g. asubstituted C₁ to C₁₂ hydrocarbyl group or an unsubstituted C₁ to C₁₂hydrocarbyl group), such as methyl, ethyl, propyl, butyl, pentyl, hexyl,phenyl, biphenyl, or an isomer thereof. In one or more embodiments, R′is a C₁ to C₂₀ alkyl or aryl, such as methyl, methyl phenyl, phenyl,biphenyl, pentamethylphenyl, tetramethylphenyl, or di-t-butylphenyl;alternatively R³ and R⁹ are selected from the group consisting of:—CH₂—SiMe₃, —CH₂—SiEt₃, —CH₂—SiPr₃, —CH₂—SiBu₃, —CH₂—SiCy₃,—CH₂—SiH(CH₃)₂, —CH₂SiPh₃, —CH₂—Si(CH₃)₂Ph, —CH₂—Si(CH₃)Ph₂,—CH₂—Si(Et)₂Ph, —CH₂—Si(Et)Ph₂, —CH₂—Si(CH₂)₃Ph, —CH₂—Si(CH₂)₄Ph,—CH₂—Si(Cy)Ph₂, or —CH₂—Si(Cy)₂Ph.

Alternatively, each X may be, independently, a halide, a hydride, analkyl group, an alkenyl group or an arylalkyl group.

Alternatively, each X is independently selected from the groupconsisting of hydrocarbyl radicals having from 1 to 20 carbon atoms,aryls, hydrides, amides, alkoxides, sulfides, phosphides, halides,dienes, amines, phosphines, ethers, and a combination thereof, (two Xsmay form a part of a fused ring or a ring system). In certainembodiments, each X is independently selected from halides, aryls and C₁to C₅ alkyl groups; for example, each X is a phenyl, methyl, ethyl,propyl, butyl, pentyl, or chloro group.

In one or more embodiments, the unbridged hafnium compound is anasymmetric catalyst, which refers to a catalyst compound where a mirrorplane cannot be drawn through the metal center and the cyclopentadienylmoieties bridged to the metal center are structurally different. Inother embodiments, the unbridged hafnium compound is a symmetriccatalyst.

Catalyst compounds represented by formula (A) can be one or more of:(Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (MeCp)(3-CH₂—SiMe₃-Cp)HfMe₂;(EtCp)(3-CH₂—SiMe₃-Cp)HfMe₂; (PrCp)(3-CH₂—SiMe₃-Cp)HfMe₂;(BuCp)(3-CH₂—SiMe₃-Cp)HfMe₂; (BzCp)(3-CH₂—SiMe₃-Cp)HfMe₂;(3-CH₂—SiMe₃-Cp)₂HfMe₂; (Me₃Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₄Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (Me₅Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (1-Me,3-Bu-Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (1-Me, 3-Ph-Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₄Cp-Pr)(3-CH₂—SiMe₃-Cp)HfMe₂; (Me₄Cp-CH₂—SiMe₃)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Me,3-CH₂—SiMe₃-Ind)₂HfMe₂; (2-Et,3-CH₂—SiMe₃-Ind)₂HfMe₂;(2-Pr,3-CH₂—SiMe₃-Ind)₂HfMe₂; (2-Bu,3-CH₂—SiMe₃-Ind)₂HfMe₂;(2-Ph,3-CH₂—SiMe₃-Ind)₂HfMe₂; (3-CH₂—SiMe₃-Ind)₂HfMe₂;(3-CH₂—SiMe₃-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (3-Me-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(3-Et-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (3-Pr-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(3-Bu-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (Cp)(3-CH₂—SiMe₃-Ind)HfMe₂;(MeCp)(3-CH₂—SiMe₃-Ind)HfMe₂; (EtCp)(3-CH₂—SiMe₃-Ind)HfMe₂;(PrCp)(3-CH₂—SiMe₃-Ind)HfMe₂; (BuCp)(3-CH₂—SiMe₃-Ind)HfMe₂;(Me₃Cp)(3-CH₂—SiMe₃-Ind)HfMe₂; (Me₄Cp)(3-CH₂—SiMe₃-Ind)HfMe₂;(Me₅Cp)(3-CH₂—SiMe₃-Ind)HfMe₂; (1-Me, 3-Bu-Cp)(3-CH₂—SiMe₃-Ind)HfMe₂;(1-Me, 3-Ph-Cp)(3-CH₂—SiMe₃-Ind)HfMe₂, (Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(MeCp)(3-CH₂—SiMe₃-Cp)HfMe₂; (EtCp)(3-CH₂—SiMe₃-Cp)HfMe₂;(PrCp)(3-CH₂—SiMe₃-Cp)HfMe₂; (BuCp)(3-CH₂—SiMe₃-Cp)HfMe₂;(BzCp)(3-CH₂—SiMe₃-Cp)HfMe₂; (3-CH₂—SiMe₃-Cp)₂HfMe₂;(Me₂Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (Me₃Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₄Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (Me₅Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(Et₂Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (Et₃Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(Et₄Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (Et₅Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(Pr₂Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (Pr₃Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(Pr₄Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (Pr₅Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(Bu₂Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (Bu₃Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(Bu₄Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (Bu₅Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(Bz₂Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (Bz₃Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(Bz₄Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (Bz₅Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(EtMe₄Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (PrMe₄Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(BuMe₄Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (PnMe₄Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(HxMe₄Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (BzMe₄Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₃)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Ph)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Ph)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMePh₂)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiPh₃)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Cy)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMeCy₂)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₄Cp-CH₂—-SiCy₃)(3-CH₂—SiMe₃-Cp)HfMe₂; (EtMe₃Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(PrMe₃Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (BuMe₃Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(BzMe₃Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (Me₃Cp-CH₂—SiMe₃)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Ph)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiMePh₂)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiPh₃)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Cy)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiMeCy₂)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiCy₃)(3-CH₂—SiMe₃-Cp)HfMe₂; (MeEtCp)(3-CH₂—SiMe₃-Cp)HfMe₂;(MePrCp)(3-CH₂—SiMe₃-Cp)HfMe₂; MeBuCp)(3-CH₂—SiMe₃-Cp)HfMe₂;(BzMeCp)(3-CH₂—SiMe₃-Cp)HfMe₂; (EtPrCp)(3-CH₂—SiMe₃-Cp)HfMe₂;(EtBuCp)(3-CH₂—SiMe₃-Cp)HfMe₂; (BzEtCp)(3-CH₂—SiMe₃-Cp)HfMe₂;(PrBuCp)(3-CH₂—SiMe₃-Cp)HfMe₂; (BzPrCp)(3-CH₂—SiMe₃-Cp)HfMe₂;(BuBzCp)(3-CH₂—SiMe₃-Cp)HfMe₂; (Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(MeCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (EtCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(PrCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (BuCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(BzCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (3-CH₂—SiMe₂Ph-Cp)₂HfMe₂;(Me₂Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (Me₃Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Me₄Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (Me₅Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Et₂Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (Et₃Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Et₄Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (Et₅Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Pr₂Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (Pr₃Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Pr₄Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (Pr₅Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Bu₂Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (Bu₃Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Bu₄Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (Bu₅Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Bz₂Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (Bz₃Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Bz₄Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (Bz₅Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(EtMe₄Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (PrMe₄Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(BuMe₄Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (BzMe₄Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₃)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Ph)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Me₄Cp-CH₂—SiMePh₂)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Me₄Cp-CH₂—SiPh₃)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Cy)(3-CH₂—SiMe₂Ph-Cp)HfCl₂;(Me₄Cp-CH₂—SiMeCy₂)(3-CH₂—SiMe₂Ph-Cp)HfCl₂;(Me₄Cp-CH₂—SiCy₃)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(EtMe₃Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (PrMe₃Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(BuMe₃Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (BzMe₃Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₃)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Ph)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Me₃Cp-CH₂—SiMePh₂)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Me₃Cp-CH₂—SiPh₃)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Cy)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Me₃Cp-CH₂—SiMeCy₂)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Me₃Cp-CH₂—SiCy₃)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(MeEtCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (MePrCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(MeBuCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (BzMeCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(EtPrCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (EtBuCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(BzEtCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (PrBuCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(BzPrCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (BuBzCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (MeCp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(EtCp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (PrCp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(BuCp)(3-CH₂—SiMePh₂-Cp)HfMe₂; ((BzCp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(3-CH₂—SiMePh₂-Cp)₂HfMe₂; (Me₂Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₃Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (Me₄Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₅Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (Et₂Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Et₃Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (Et₄Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Et₅Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (Pr₂Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Pr₃Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (Pr₄Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Pr₅Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (Bu₂Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Bu₃Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (Bu₄Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Bu₅Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (Bz₂Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Bz₃Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (Bz₄Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Bz₅Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (EtMe₄Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(PrMe₄Cp)(3—CH₂—SiMePh₂-Cp)HfMe₂; (BuMe₄Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(PnMe₄Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (HxMe₄Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(BzMe₄Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₃)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Ph)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiMePh₂)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiPh₃)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Cy)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiMeCy₂)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiCy₃)(3-CH₂—SiMePh₂-Cp)HfMe₂;(EtMe₃Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (PrMe₃Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(BuMe₃Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (BzMe₃Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₃)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Ph)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiMePh₂)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiPh₃)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Cy)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiMeCy₂)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiCy₃)(3-CH₂—SiMePh₂-Cp)HfMe₂;(MeEtCp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (MePrCp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(MeBuCp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (BzMeCp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(EtPrCp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (EtBuCp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(BzEtCp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (PrBuCp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(BzPrCp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (BuBzCp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (MeCp)(3-CH₂—SiPh₃-Cp)HfMe₂;(EtCp)(3-CH₂—SiPh₃-Cp)HfMe₂; (PrCp)(3-CH₂—SiPh₃-Cp)HfMe₂;(BuCp)(3-CH₂—SiPh₃-Cp)HfMe₂; (BzCp)(3-CH₂—SiPh₃-Cp)HfMe₂;(3-CH₂—SiPh₃-Cp)₂HfMe₂; (Me₂Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₃Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (Me₄Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₅Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (Et₂Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(Et₃Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (Et₄Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(Et₅Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (Pr₂Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(Pr₃Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (Pr₄Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(Pr₅Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (Bu₂Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(Bu₃Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (Bu₄Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(Bu₅Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (Bz₂Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(Bz₃Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (Bz₄Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(Bz₅Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (EtMe₄Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(PrMe₄Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (BuMe₄Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(BzMe₄Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (Me₄Cp-CH₂—SiMe₃)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Ph)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMePh₂)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiPh₃)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Cy)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMeCy₂)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiCy₃)(3-CH₂—SiPh₃-Cp)HfMe₂; (EtMe₃Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(PrMe₃Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (BuMe₃Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(BzMe₃Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (Me₃Cp-CH₂—SiMe₃)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Ph)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiMePh₂)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiPh₃)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Cy)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiMeCy₂)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiCy₃)(3-CH₂—SiPh₃-Cp)HfMe₂; (MeEtCp)(3-CH₂—SiPh₃-Cp)HfMe₂;(MePrCp)(3-CH₂—SiPh₃-Cp)HfMe₂; (MeBuCp)(3-CH₂—SiPh₃-Cp)HfMe₂;(BzMeCp)(3-CH₂—SiPh₃-Cp)HfMe₂; (EtPrCp)(3-CH₂—SiPh₃-Cp)HfMe₂;(EtBuCp)(3-CH₂—SiPh₃-Cp)HfMe₂; (BzEtCp)(3-CH₂—SiPh₃-Cp)HfMe₂;(PrBuCp)(3-CH₂—SiPh₃-Cp)HfMe₂; (BzPrCp)(3-CH₂—SiPh₃-Cp)HfMe₂;(BuBzCp)(3-CH₂—SiPh₃-Cp)HfMe₂; (Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(MeCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (EtCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(PrCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (BuCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(BzCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (3-CH₂—SiCyMe₂-Cp)₂HfMe₂;(Me₂Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (Me₃Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₄Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (Me₅Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Et₂Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (Et₃Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Et₄Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (Et₅Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Pr₂Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (Pr₃Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Pr₄Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (Pr₅Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Bu₂Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (Bu₃Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Bu₄Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (Bu₅Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Bz₂Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (Bz₃Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Bz₄Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (Bz₅Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(EtMe₄Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (PrMe₄Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(BuMe₄Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (BzMe₄Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₃)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiCyMe₂Ph)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiMePh₂)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiPh₃)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Cy)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiMeCy₂)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiCy₃)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(EtMe₃Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (PrMe₃Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(BuMe₃Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (BzMe₃Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₃)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Ph)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiMePh₂)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiPh₃)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Cy)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiMeCy₂)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiCy₃)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(MeEtCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (MePrCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(MeBuCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (BzMeCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(EtPrCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (EtBuCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(BzEtCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (PrBuCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(BzPrCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (BuBzCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (MeCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(EtCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (PrCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(BuCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (BzCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(3-CH₂—SiCy₂Me-Cp)₂HfMe₂; (Me₂Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₃Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (Me₄Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₅Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (Et₂Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Et₃Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (Et₄Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Et₅Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (Pr₂Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Pr₃Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (Pr₄Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Pr₅Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (Bu₂Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Bu₃Cp)(3-CH₂—SiCy₂Me-Cp)HfCl₂; (Bu₄Cp)(3-CH₂—SiCy₂Me-Cp)HfCl₂;(Bu₅Cp)(3-CH₂—SiCy₂Me-Cp)HfCl₂; (Bz₂Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Bz₃Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (Bz₄Cp)(3-CH₂—SiCy₂Me-Cp)HfCl₂;(Bz₅Cp)(3-CH₂—SiCy₂Me-Cp)HfCl₂; (EtMe₄Cp)(3-CH₂—SiCy₂Me-Cp)HfCl₂;(PrMe₄Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (BuMe₄Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(BzMe₄Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₃)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Ph)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₄Cp-CH₂—SiMePh₂)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₄Cp-CH₂—SiPh₃)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Cy)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₄Cp-CH₂—SiMeCy₂)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₄Cp-CH₂—SiCy₃)(3-CH₂-Cy₂Me-Cp)HfMe₂;(EtMe₃Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (PrMe₃Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(BuMe₃Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (BzMe₃Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₃)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Ph)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₃Cp-CH₂—SiMePh₂)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₃Cp-CH₂—SiPh₃)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Cy)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₃Cp-CH₂—SiMeCy₂)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₃Cp-CH₂—SiCy₃)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(MeEtCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (MePrCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(MeBuCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (BzMeCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(EtPrCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (EtBuCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(BzEtCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (PrBuCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(BzPrCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (BuBzCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (MeCp)(3-CH₂—SiCy₃-Cp)HfMe₂;(EtCp)(3-CH₂—SiCy₃-Cp)HfMe₂; (PrCp)(3-CH₂—SiCy₃-Cp)HfMe₂;(BuCp)(3-CH₂—SiCy₃-Cp)HfMe₂ (BzCp)(3-CH₂-SiCy₃-Cp)HfMe₂;(3-CH₂—SiCy₃-Cp)₂HfMe₂; (Me₂Cp)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₃Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (Me₄Cp)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₅Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (Et₂Cp)(3-CH₂—SiCy₃-Cp)HfMe₂;(Et₃Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (Et₄Cp)(3-CH₂—SiCy₃-Cp)HfMe₂;(Et₅Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (Pr₂Cp)(3-CH₂—SiCy₃-Cp)HfMe₂;(Pr₃Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (Pr₄Cp)(3-CH₂—SiCy₃-Cp)HfMe₂;(Pr₅Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (Bu₂Cp)(3-CH₂—SiCy₃-Cp)HfMe₂;(Bu₃Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (Bu₄Cp)(3-CH₂—SiCy₃-Cp)HfMe₂;(Bu₅Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (Bz₂Cp)(3-CH₂—SiCy₃-Cp)HfMe₂;(Bz₃Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (Bz₄Cp)(3-CH₂—SiCy₃-Cp)HfMe₂;(Bz₅Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (EtMe₄Cp)(3-CH₂—SiCy₃-Cp)HfMe₂;(PrMe₄Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (BuMe₄Cp)(3-CH₂—SiCy₃-Cp)HfMe₂;(BzMe₄Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (Me₄Cp-CH₂—SiMe₃)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Ph)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMePh₂)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiPh₃)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Cy)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMeCy₂)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiCy₃)(3-CH₂—SiCy₃-Cp)HfMe₂; (EtMe₃Cp)(3-CH₂—SiCy₃-Cp)HfMe₂;(PrMe₃Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (BuMe₃Cp)(3-CH₂—SiCy₃-Cp)HfMe₂;(BzMe₃Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (Me₃Cp-CH₂—SiMe₃)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Ph)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiMePh₂)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiPh₃)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Cy)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiMeCy₂)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiCy₃)(3-CH₂—SiCy₃-Cp)HfMe₂; (MeEtCp)(3-CH₂—SiCy₃-Cp)HfMe₂;(MePrCp)(3-CH₂—SiCy₃-Cp)HfMe₂; (MeBuCp)(3-CH₂—SiCy₃-Cp)HfMe₂;(BzMeCp)(3-CH₂—SiCy₃-Cp)HfMe₂; (EtPrCp)(3-CH₂—SiPCy-Cp)HfMe₂;(EtBuCp)(3-CH₂—SiCy₃-Cp)HfMe₂; (BzEtCp)(3-CH₂—SiCy₃-Cp)HfMe₂;(PrBuCp)(3-CH₂—SiCy₃-Cp)HfMe₂; (BzPrCp)(3-CH₂—SiCy₃-Cp)HfMe₂;(BuBzCp)(3-CH₂—SiCy₃-Cp)HfMe₂; (2-Me,3-CH₂—SiMe₃-Ind)₂HfMe₂;(2-Et,3-CH₂—SiMe₃-Ind)₂HfMe₂; (2-Pr,3-CH₂—SiMe₃-Ind)₂HfMe₂;(2-Bu,3-CH₂—SiMe₃-Ind)₂HfMe₂; (2-Ph,3-CH₂—SiMe₃-Ind)₂HfMe₂;(2-Bz,3-CH₂—SiMe₃-Ind)₂HfMe₂; (2-Me,3-CH₂—SiMe₂Ph-Ind)₂HfMe₂;(2-Et,3-CH₂—SiMe₂Ph-Ind)₂HfMe₂; (2-Pr,3-CH₂—SiMe₂Ph-Ind)₂HfMe₂;(2-Bu,3-CH₂—SiMe₂Ph-Ind)₂HfMe₂; (2-Ph,3-CH₂—SiMe₂Ph-Ind)₂HfMe₂;(2-Bz,3-CH₂—SiMe₂Ph-Ind)₂HfMe₂; (2-Me,3-CH₂—SiMePh₂-Ind)₂HfMe₂;(2-Et,3-CH₂—SiMePh₂-Ind)₂HfMe₂; (2-Pr,3-CH₂—SiMePh₂-Ind)₂HfMe₂;(2-Bu,3-CH₂—SiMePh₂-Ind)₂HfMe₂; (2-Ph,3-CH₂—SiMePh₂-Ind)₂HfMe₂; (2-Bz,3-CH₂—SiMePh₂-Ind)₂HfMe₂; (2-Me,3-CH₂—SiPh₃-Ind)₂HfMe₂;(2-Et,3-CH₂—SiPh₃-Ind)₂HfMe₂; (2-Pr,3-CH₂—SiPh₃-Ind)₂HfMe₂;(2-Bu,3-CH₂—SiPh₃-Ind)₂HfMe₂; (2-Ph,3-CH₂—SiPh₃-Ind)₂HfMe₂;(2-Bz,3-CH₂—SiPh₃-Ind)₂HfMe₂; (2-Me,3-CH₂—SiCyMe₂-Ind)₂HfMe₂; (2-Et,3—CH₂—SiCyMe₂-Ind)₂HfMe₂; (2-Pr,3-CH₂—SiCyMe₂-Ind)₂HfMe₂;(2-Bu,3-CH₂—SiCyMe₂-Ind)₂HfMe₂; (2-Ph,3-CH₂—SiCyMe₂-Ind)₂HfMe₂;(2-Bz,3-CH₂—SiCyMe₂-Ind)₂HfMe₂; (2-Me,3-CH₂—SiCy₂Me-Ind)₂HfMe₂;(2-Et,3-CH₂—SiCy₂Me-Ind)₂HfMe₂; (2-Pr,3-CH₂—SiCy₂Me-Ind)₂HfMe₂;(2-Bu,3-CH₂—SiCy₂Me-Ind)₂HfMe₂; (2-Ph,3-CH₂—SiCy₂Me-Ind)₂HfMe₂;(2-Bz,3-CH₂—SiCy₂Me-Ind)₂HfMe₂; (2-Me,3-CH₂—SiCy₃-Ind)₂HfMe₂;(2-Et,3-CH₂—SiCy₃-Ind)₂HfMe₂; (2-Pr,3-CH₂—SiCy₃-Ind)₂HfMe₂;(2-Bu,3-CH₂—SiCy₃-Ind)₂HfMe₂; (2-Ph,3-CH₂—SiCy₃-Ind)₂HfMe₂;(2-Bz,3-CH₂—SiCy₃-Ind)₂HfMe₂;(2-Me,3-CH₂—SiMe₃-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (2-Et,3-CH₂—SiMe₃-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Pr,3-CH₂—SiMe₃-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Bu,3-CH₂—SiMe₃-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Pn,3-CH₂—SiMe₃-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Hx,3-CH₂—SiMe₃-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Ph,3-CH₂—SiMe₃-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Me,3-CH₂—SiMe₂Ph-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (2-Et,3-CH₂—SiMe₂Ph-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Pr,3-CH₂—SiMe₂Ph-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Bu,3-CH₂—SiMe₂Ph-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (2-Pn,3-CH₂—SiMe₂Ph-Ind)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(2-Hx,3-CH₂—SiMe₂Ph-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Ph,3-CH₂—SiMe₂Ph-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Me,3-CH₂—SiMePh₂-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Et,3-CH₂—SiMePh₂-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (2-Pr,3-CH₂—SiMePh₂-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Bu,3-CH₂—SiMePh₂-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Pn,3-CH₂—SiMePh₂-Ind)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (2-Hx,3-CH₂—SiMePh₂-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (2-Ph,3-CH₂—SiMePh₂-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Me,3-CH₂—SiPh₃-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Et,3-CH₂—SiPh₃-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Pr,3-CH₂—SiPh₃-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Bu,3-CH₂—SiPh₃-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Pn,3-CH₂—SiPh₃-Ind)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(2-Hx,3-CH₂—SiPh₃-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (2-Ph,3-CH₂—SiPhi-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Me,3-CH₂—SiCyMe₂-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Et,3-CH₂—SiCyMe₂-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Pr,3-CH₂—SiCyMe₂-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Bu,3-CH₂—SiCyMe₂-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Pn,3-CH₂—SiCyMe₂-Ind)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(2-Hx,3-CH₂—SiCyMe₂-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Ph,3-CH₂—SiCyMe₂-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂, and the alkyl or halideversions thereof where the Me₂ is substituted with Bz₂, Et₂, Phe, Cl₂,Br₂ or I₂.

Unbridged Zirconium Metallocene

In one or more embodiments, the unbridged zirconium metallocene compoundmay be represented by the formula Cp^(A)Cp_(B)ZrX′_(n), wherein Cp^(A)and Cp^(B) may each be independently selected from the group consistingof cyclopentadienyl ligands and ligands isolobal to cyclopentadienyl,either or both Cp^(A) and Cp^(B) may contain heteroatoms, and either orboth Cp^(A) and Cp^(B) may be substituted; wherein X′ may be any leavinggroup; wherein n is 0, 1, or 2.

Unbridged zirconium metallocenes useful herein are further representedby the formula (C):Cp_(m)ZrX_(q)  (C),wherein each Cp is, independently, a cyclopentadienyl group (such ascyclopentadiene, indene or fluorene) which may be substituted orunsubstituted, X is a leaving group (such as a halide, a hydride, analkyl group, an alkenyl group or an arylalkyl group), and m=1 or 2, n=0,1, 2 or 3, q=0, 1, 2, or 3, and the sum of m+q is equal to the oxidationstate of the transition metal. In some embodiments, m is 2.

In an embodiment each X may be, independently, a halide, a hydride, analkyl group, an alkenyl group or an arylalkyl group.

Alternately, each X is, independently, selected from the groupconsisting of hydrocarbyl radicals having from 1 to 20 carbon atoms,aryls, hydrides, amides, alkoxides, sulfides, phosphides, halides,dienes, amines, phosphines, ethers, and a combination thereof, (two X'smay form a part of a fused ring or a ring system). In particularembodiments, each X is independently selected from halides, aryls and C₁to C₅ alkyl groups. In particular embodiments, each X is a phenyl,methyl, ethyl, propyl, butyl, pentyl, or chloro group.

Typically, each Cp group is, independently, a substituted orunsubstituted cyclopentadiene, a substituted or unsubstituted indene, ora substituted or unsubstituted fluorene.

Independently, each Cp group may be substituted with a combination ofsubstituent groups R. Non-limiting examples of substituent groups Rinclude one or more from the group selected from hydrogen, or linear,branched alkyl radicals, or alkenyl radicals, alkynyl radicals,cycloalkyl radicals or aryl radicals, acyl radicals, alkoxy radicals,aryloxy radicals, alkylthio radicals, dialkylamino radicals,alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbamoyl radicals,alkyl- or dialkyl-carbamoyl radicals, acyloxy radicals, acylaminoradicals, aroylamino radicals, straight, branched or cyclic, alkyleneradicals, or combination thereof. In particular embodiments, substituentgroups R have up to 50 non-hydrogen atoms, preferably from 1 to 30carbon, that can also be substituted with halogens or heteroatoms or thelike. Non-limiting examples of alkyl substituents R include methyl,ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl orphenyl groups and the like, including all their isomers, for example,tertiary butyl, isopropyl and the like. Other hydrocarbyl radicalsinclude fluoromethyl, fluoroethyl, difluoroethyl, iodopropyl, bromohexylchlorobenzyl and hydrocarbyl substituted organometalloid radicalsincluding trimethylsilyl, trimethylgermyl, methyldiethylsilyl and thelike; and halocarbyl-substituted organometalloid radicals includingtris(trifluoromethyl)-silyl, methylbis(difluoromethyl)silyl,bromomethyldimethylgermyl and the like; and disubstituted boron radicalsincluding dimethylboron for example; and disubstituted pnictogenradicals including dimethylamine, dimethylphosphine, diphenylamine,methylphenylphosphine, chalcogen radicals including methoxy, ethoxy,propoxy, phenoxy, methylsulfide and ethylsulfide. Non-hydrogensubstituents R include the atoms carbon, silicon, boron, aluminum,nitrogen, phosphorus, oxygen, tin, sulfur, germanium and the like,including olefins such as, but not limited to, olefinically unsaturatedsubstituents including vinyl-terminated ligands, for example but-3-enyl,prop-2-enyl, hex-5-enyl and the like. Also, at least two R groups,including two adjacent R groups, may be joined to form a ring structurehaving from 3 to 30 atoms selected from carbon, nitrogen, oxygen,phosphorus, silicon, germanium, aluminum, boron or a combinationthereof.

In an embodiment of the Cp group, the substituent(s) R are,independently, hydrocarbyl groups, heteroatoms, or heteroatom containinggroups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, undecyl, dodecyl or an isomer thereof, N, O, S, P,or a C₁ to C₂₀ hydrocarbyl substituted with an N, O, S and or Pheteroatom or heteroatom containing group (typically having up to 12atoms, including the N, O, S and P heteroatoms).

Non-limiting examples of Cp groups include cyclopentadienyl ligands,cyclopentaphenanthreneyl ligands, indenyl ligands, benzindenyl ligands,fluorenyl ligands, octahydrofluorenyl ligands, cyclooctatetraenylligands, cyclopentacyclododecene ligands, azenyl ligands, azuleneligands, pentalene ligands, phosphoyl ligands, phosphinimine ligands (WO99/40125), pyrrolyl ligands, pyrazolyl ligands, carbazolyl ligands,borabenzene ligands and the like, including hydrogenated versionsthereof, for example tetrahydroindenyl ligands. In another embodiment,each Cp may, independently comprise one or more heteroatoms, forexample, nitrogen, silicon, boron, germanium, sulfur and phosphorus, incombination with carbon atoms to form an open, acyclic, or preferably afused, ring or ring system, for example, a heterocyclopentadienylancillary ligand. Other Cp ligands include but are not limited toporphyrins, phthalocyanines, corrins and other polyazamacrocycles.

In another aspect, the unbridged metallocene catalyst component isrepresented by the formula (D):Cp^(A)Cp^(B)ZrX_(q)  (D),wherein X and q are as described above, preferably q is 1 or 2, and eachCp^(A) and Cp^(B) in formula (D) is independently as defined for Cpabove and may be the same or different cyclopentadienyl ligands orligands isolobal to cyclopentadienyl, either or both of which maycontain heteroatoms and either or both of which may be substituted by agroup R. In one embodiment, Cp^(A) and Cp^(B) are independently selectedfrom the group consisting of cyclopentadienyl, indenyl,tetrahydroindenyl, fluorenyl, and substituted derivatives of each.

Independently, each Cp^(A) and Cp^(B) of formula (D) may beunsubstituted or substituted with any one or combination of substituentgroups R. Non-limiting examples of substituent groups R as used instructure (D) include hydrogen radicals, hydrocarbyls, lowerhydrocarbyls, substituted hydrocarbyls, heterohydrocarbyls, alkyls,lower alkyls, substituted alkyls, heteroalkyls, alkenyls, loweralkenyls, substituted alkenyls, heteroalkenyls, alkynyls, loweralkynyls, substituted alkynyls, heteroalkynyls, alkoxys, lower alkoxys,aryloxys, hydroxyls, alkylthios, lower alkyls thios, arylthios, thioxys,aryls, substituted aryls, heteroaryls, aralkyls, aralkylenes, alkaryls,alkarylenes, halides, haloalkyls, haloalkenyls, haloalkynyls,heteroalkyls, heterocycles, heteroaryls, heteroatom-containing groups,silyls, boryls, phosphinos, phosphines, aminos, amines, cycloalkyls,acyls, aroyls, alkylthiols, dialkylamines, alkylamidos, alkoxycarbonyls,aryloxycarbonyls, carbomoyls, alkyl- and dialkyl-carbamoyls, acyloxys,acylaminos, aroylaminos, and combinations thereof.

More particular, non-limiting examples of alkyl substituents Rassociated with formula (D) includes methyl, ethyl, propyl, butyl,pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl, phenyl, methylphenyl,and tert-butylphenyl groups and the like, including all their isomers,for example, tertiary-butyl, isopropyl, and the like. Other possibleradicals include substituted alkyls and aryls such as, for example,fluoromethyl, fluoroethyl, difluoroethyl, iodopropyl, bromohexyl,chlorobenzyl and hydrocarbyl substituted organometalloid radicalsincluding trimethylsilyl, trimethylgermyl, methyldiethylsilyl and thelike; and halocarbyl-substituted organometalloid radicals includingtris(trifluoromethyl)silyl, methylbis(difluoromethyl)silyl,bromomethyldimethylgermyl and the like; and disubstituted boron radicalsincluding dimethylboron, for example; and disubstituted Group 15radicals including dimethylamine, dimethylphosphine, diphenylamine,methylphenylphosphine, Group 16 radicals including methoxy, ethoxy,propoxy, phenoxy, methylsulfide and ethylsulfide. Other substituents Rinclude olefins such as, but not limited to, olefinically unsaturatedsubstituents including vinyl-terminated ligands, for example, 3-butenyl,2-propenyl, 5-hexenyl and the like. In one embodiment, at least two Rgroups, two adjacent R groups in one embodiment, are joined to form aring structure having from 3 to 30 atoms selected from the groupconsisting of carbon, nitrogen, oxygen, phosphorous, silicon, germanium,aluminum, boron and combinations thereof. Also, a substituent group R,such as 1-butanyl, may form a bonding association to the element M.

The ligands Cp^(A) and Cp^(B) of formula (D) are different from eachother in one embodiment, and the same in another embodiment.

It is contemplated that the metallocene catalyst components describedabove include their structural or optical or enantiomeric isomers(racemic mixture), and may be a pure enantiomer in one embodiment.

The unbridged metallocene catalyst component may comprise anycombination of any embodiments described herein.

Suitable unbridged metallocenes useful herein include, but are notlimited to, the metallocenes disclosed and referenced in the U.S.patents cited above, as well as those disclosed and referenced in U.S.Pat. Nos. 7,179,876; 7,169,864; 7,157,531; 7,129,302; 6,995,109;6,958,306; 6,884,748; 6,689,847; U.S. Publication 2007/0055028, and PCTPublication Nos. WO 97/22635; WO 00/699/22; WO 01/30860; WO 01/30861; WO02/46246; WO 02/50088; WO 04/026921; and WO 06/019494, all fullyincorporated herein by reference. Additional catalysts suitable for useherein include those referenced in U.S. Pat. Nos. 6,309,997; 6,265,338;U.S. Publication No. 2006/019925, and the following articles: Chem Rev2000, 100, 1253; Resconi; Chem Rev 2003, 103, 283; Chem Eur. J. 2006,12, 7546 Mitsui; J Mol Catal A 2004, 213, 141; Macromol Chem Phys, 2005,206, 1847; and J Am Chem Soc 2001, 123, 6847.

Exemplary unbridged zirconium metallocene compounds useful herein areinclude bis(cyclopentadienyl)zirconium dichloride;bis(cyclopentadienyl)zirconium dimethyl;bis(n-butylcyclopentadienyl)zirconium dichloride;bis(n-butylcyclopentadienyl)zirconium dimethyl;bis(pentamethylcyclopentadienyl)zirconium dichloride;bis(pentamethylcyclopentadienyl)zirconium dimethyl;bis(pentamethylcyclopentadienyl)zirconium dimethyl;bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride;bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dimethyl;bis(1-methyl-3-phenylcyclopentadienyl)zirconium dichloride;bis(1-methyl-3-phenylcyclopentadienyl)zirconium dimethyl;bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dimethyl;bis(indenyl)zirconium dichloride, bis(indenyl)zirconium dimethyl;bis(tetrahydro-1-indenyl)zirconium dichloride;bis(tetrahydro-1-indenyl)zirconium dimethyl; (n-propylcyclopentadienyl)(pentamethyl cyclopentadienyl)zirconium dichloride;(n-propyl cyclopentadienyl)(pentamethyl cyclopentadienyl)zirconiumdimethyl; rac/meso-(1-Ethylindenyl)zirconium dichloride;rac/meso-(1-Ethylindenyl)zirconium dimethyl;rac/meso-(1-methylindenyl)zirconium dichloride;rac/meso-(1-methylindenyl)zirconium dimethyl;rac/meso-(1-propylindenyl)zirconium dichloride;rac/meso-(1-propylindenyl)zirconium dimethyl;rac/meso-(1-butylindenyl)zirconium dichloride;rac/meso-(1-butylindenyl)zirconium dimethyl; meso-(1ethylindenyl)zirconium dichloride; meso-(1ethylindenyl) zirconium dimethyl;(1-methylindenyl)(pentamethyl cyclopentadienyl) zirconium dichloride;and (1-methylindenyl)(pentamethyl cyclopentadienyl) zirconium dimethyl.

In one or more embodiments, useful unbridged metallocene compoundsinclude bis(cyclopentadienyl)zirconium dichloride;bis(n-butylcyclopentadienyl)zirconium dichloride;bis(n-butylcyclopentadienyl)zirconium dimethyl;bis(pentamethylcyclopentadienyl)zirconium dichloride;bis(pentamethylcyclopentadienyl)zirconium dimethyl;bis(pentamethylcyclopentadienyl)hafnium dichloride;bis(pentamethylcyclopentadienyl)zirconium dimethyl;bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride;bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dimethyl;bis(1-methyl-3-n-butylcyclopentadienyl)hafnium dichloride;bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dimethyl;bis(indenyl)zirconium dichloride, bis(indenyl)zirconium dimethyl;bis(tetrahydro-1-indenyl)zirconium dichloride;bis(tetrahydro-1-indenyl)zirconium dimethyl; (n-propylcyclopentadienyl)(pentamethyl cyclopentadienyl)zirconium dichloride;(n-propyl cyclopentadienyl)(pentamethyl cyclopentadienyl)zirconiumdimethyl; Rac/meso-(1-Ethylindenyl)zirconium dichloride;Rac/meso-(1-methylindenyl)zirconium dichloride;Rac/meso-(1-propylindenyl)zirconium dichloride; Meso-(1ethylindenyl)zirconium dichloride, and (1-Methylindenyl)(pentamethylcyclopentadienyl).

For purposes of this specification one metallocene catalyst compound isconsidered different from another if they differ by at least one atom.For example “bisindenyl zirconium dichloride” is different from“(indenyl)(2-methylindenyl) zirconium dichloride.” Catalyst compoundsthat differ only by isomer are considered the same for purposes of thisinvention, e.g., rac-dimethylsilylbis(2-methyl 4-phenyl)hafnium dimethylis considered to be the same as meso-dimethylsilylbis(2-methyl4-phenyl)hafnium dimethyl. Thus, as used herein, a single, bridged,asymmetrically substituted metallocene catalyst component having aracemic and/or meso isomer does not, itself, constitute two differentbridged, metallocene catalyst components.

Catalyst Ratios

In one or more embodiments, two transition metal compounds may be usedin any ratio. In particular embodiments, molar ratios of (A) bridgedhafnium transition metal compound to (B) unbridged transition metalcompound fall within the range of (A:B) 1:1000 to 1000:1, alternatively1:100 to 500:1, alternatively 1:10 to 200:1, alternatively 1:1 to 100:1,and alternatively 1:1 to 75:1, and alternatively 5:1 to 50:1. Theparticular ratio chosen will depend on the exact catalyst compoundschosen, the method of activation, and the end product desired. In aparticular embodiment, when using the two catalyst compounds, where bothare activated with the same activator, useful mole percents, based uponthe molecular weight of the catalyst compounds, are 10 to 99.9% A to 0.1to 90% B, alternatively 25 to 99% A to 0.5 to 50% B, alternatively 50 to99% A to 1 to 25% B, and alternatively 75 to 99% A to 1 to 10% B.

Support Material

In embodiments of the invention herein, the catalyst systems comprise asupport material. In particular embodiments, the support material is aporous support material, for example, talc, and inorganic oxides. Othersupport materials include zeolites, clays, organoclays, or any otherorganic or inorganic support material, or mixtures thereof. As usedherein, “support” and “support material” are used interchangeably.

In one or more embodiments, the support material is an inorganic oxidein a finely divided form. Suitable inorganic oxide materials for use inthe supported catalyst systems herein include Groups 2, 4, 13, and 14metal oxides such as silica, alumina, and mixtures thereof. Otherinorganic oxides that may be employed, either alone or in combination,with the silica or alumina are magnesia, titania, zirconia, and thelike. Other suitable support materials, however, can be employed, forexample, finely divided functionalized polyolefins such as finelydivided polyethylene. Particularly useful supports include magnesia,titania, zirconia, montmorillonite, phyllosilicate, zeolites, talc,clays, and the like. Also, combinations of these support materials maybe used, for example, silica-chromium, silica-alumina, silica-titania,and the like. Particular support materials include Al₂O₃, ZrO₂, SiO₂,and combinations thereof, more preferably, SiO₂, Al₂O₃, or SiO₂/Al₂O₃.

In one or more embodiments, the support material, particularly where itis an inorganic oxide, has a surface area in the range of from about 10m²/g to about 700 m²/g, pore volume in the range of from about 0.1 cc/gto about 4.0 cc/g, and average particle size in the range of from about5 μm to about 500 μm. In other embodiments, the surface area of thesupport material is in the range of from about 50 m²/g to about 500m²/g, pore volume of from about 0.5 cc/g to about 3.5 cc/g, and averageparticle size of from about 10 μm to about 200 μm. In yet otherembodiments, the surface area of the support material is in the range offrom about 100 m²/g to about 400 m²/g, pore volume from about 0.8 cc/gto about 3.0 cc/g, and average particle size is from about 5 μm to about100 μm. The average pore size of the support material useful in theinvention is in the range of from 10 to 1,000 Å, in other embodiments 50to about 500 Å, and in other embodiments 75 to about 350 Å. In someembodiments, the support material is a high surface area, amorphoussilica (surface area ≥300 m²/gm, pore volume ≥1.65 cm³/gm), and ismarketed under the tradenames of DAVISON 952 or DAVISON 955 by theDavison Chemical Division of W. R. Grace and Company, are particularlyuseful. In other embodiments, DAVIDSON 948 is used.

In some embodiments of this invention, the support material may be dry,that is, free of absorbed water. Drying of the support material can beachieved by heating or calcining at about 100° C. to about 1000° C.,preferably, at least about 600° C. When the support material is silica,it is typically heated to at least 200° C., such as about 200° C. toabout 850° C., or at about 600° C.; and for a time of about 1 minute toabout 100 hours, from about 12 hours to about 72 hours, or from about 24hours to about 60 hours. The calcined support material of particularembodiments has at least some reactive hydroxyl (OH) groups.

In certain embodiments, the support material is fluorided. Fluoridingagent containing compounds may be any compound containing a fluorineatom. Particularly desirable are inorganic fluorine containing compoundsare selected from the group consisting of NH₄BF₄, (NH₄)₂SiF₆, NH₄PF₆,NH₄F, (NH₄)₂TaF₇, NH₄NbF₄, (NH₄)₂GeF₆, (NH₄)₂SmF₆, (NH₄)₂TiF₆,(NH₄)₂ZrF₆, MoF₆, ReF₆, GaF₃, SO₂ClF, F₂, SiF₄, SF₆, ClF₃, ClF₅, BrF₅,IF₇, NF₃, HF, BF₃, NHF₂ and NH₄HF₂. Of these, ammoniumhexafluorosilicate and ammonium tetrafluoroborate are useful.Combinations of these compounds may also be used.

Ammonium hexafluorosilicate and ammonium tetrafluoroborate fluorinecompounds are typically solid particulates as are the silicon dioxidesupports. A desirable method of treating the support with the fluorinecompound is to dry mix the two components by simply blending at aconcentration of from 0.01 to 10.0 millimole F/g of support, desirablyin the range of from 0.05 to 6.0 millimole F/g of support, and mostdesirably in the range of from 0.1 to 3.0 millimole F/g of support. Thefluorine compound can be dry mixed with the support either before orafter charging to a vessel for dehydration or calcining the support.Accordingly, the fluorine concentration present on the support is in therange of from 0.1 to 25 wt %, alternately from 0.19 to 19 wt %,alternately from 0.6 to 3.5 wt %, based upon the weight of the support.

The above two metal catalyst components described herein are generallydeposited on the support material at a loading level of 10-100micromoles of metal per gram of solid support; alternately 20-80micromoles of metal per gram of solid support; or 40-60 micromoles ofmetal per gram of support. But greater or lesser values may be usedprovided that the total amount of solid complex does not exceed thesupport's pore volume.

Activators

The supported catalyst systems may be formed by combining the above twometal catalyst components with activators in any manner known from theliterature including by supporting them for use in slurry or gas phasepolymerization. Activators are defined to be any compound which canactivate any one of the catalyst compounds described above by convertingthe neutral metal compound to a catalytically active metal compoundcation. Non-limiting activators, for example, include alumoxanes,aluminum alkyls, ionizing activators, which may be neutral or ionic, andconventional-type cocatalysts. Particular activators typically includealumoxane compounds, modified alumoxane compounds, and ionizing anionprecursor compounds that abstract a reactive, σ-bound, metal ligandmaking the metal compound cationic and providing a charge-balancingnoncoordinating or weakly coordinating anion.

Alumoxane Activators

Alumoxane activators are utilized as activators in the catalyst systemsdescribed herein. Alumoxanes are generally oligomeric compoundscontaining —Al(R¹)—O— sub-units, where R¹ is an alkyl group. Examples ofalumoxanes include methylalumoxane (MAO), modified methylalumoxane(MMAO), ethylalumoxane and isobutylalumoxane. Alkylalumoxanes andmodified alkylalumoxanes are suitable as catalyst activators,particularly when the abstractable ligand is an alkyl, halide, alkoxideor amide. Mixtures of different alumoxanes and modified alumoxanes mayalso be used. It may be preferable to use a visually clearmethylalumoxane. A cloudy or gelled alumoxane can be filtered to producea clear solution or clear alumoxane can be decanted from the cloudysolution. A useful alumoxane is a modified methyl alumoxane (MMAO)cocatalyst type 3A (commercially available from Akzo Chemicals, Inc.under the trade name Modified Methylalumoxane type 3A, covered underpatent number U.S. Pat. No. 5,041,584).

When the activator is an alumoxane (modified or unmodified), someembodiments select the maximum amount of activator typically at up to a5000-fold molar excess Al/M over the catalyst compound (per metalcatalytic site). The minimum activator-to-catalyst-compound is a 1:1molar ratio. Alternate preferred ranges include from 1:1 to 500:1,alternately from 1:1 to 200:1, alternately from 1:1 to 100:1, oralternately from 1:1 to 50:1.

In an alternate embodiment, little or no alumoxane is used in thepolymerization processes described herein. Preferably, alumoxane ispresent at zero mol %, alternately the alumoxane is present at a molarratio of aluminum to catalyst compound transition metal less than 500:1,preferably less than 300:1, preferably less than 100:1, preferably lessthan 1:1.

Non Coordinating Anion Activators

The term “non-coordinating anion” (NCA) means an anion which either doesnot coordinate to a cation or which is only weakly coordinated to acation thereby remaining sufficiently labile to be displaced by aneutral Lewis base. “Compatible” non-coordinating anions are those whichare not degraded to neutrality when the initially formed complexdecomposes. Further, the anion will not transfer an anionic substituentor fragment to the cation so as to cause it to form a neutral transitionmetal compound and a neutral by-product from the anion. Non-coordinatinganions useful in accordance with this invention are those that arecompatible, stabilize the transition metal cation in the sense ofbalancing its ionic charge at +1, and yet retain sufficient lability topermit displacement during polymerization.

It is within the scope of this invention to use an ionizing activator,neutral or ionic, such as tri (n-butyl) ammonium tetrakis(pentafluorophenyl) borate, a tris perfluorophenyl boron metalloidprecursor or a tris perfluoronaphthyl boron metalloid precursor,polyhalogenated heteroborane anions (WO 98/43983), boric acid (U.S. Pat.No. 5,942,459), or combination thereof. It is also within the scope ofthis invention to use neutral or ionic activators alone or incombination with alumoxane or modified alumoxane activators.

For descriptions of useful activators please see U.S. Pat. Nos.8,658,556 and 6,211,105.

Particular activators include N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorophenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(perfluorophenyl)borate, [Me₃NH⁺][B(C₆F₅)₄ ⁻],1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium;and [Me₃NH⁺][B(C₆F₅)₄ ⁻],1-(4-(tris(pentafluorophenyOborate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium; and sodium tetrakis(pentafluorophenyl)borate, potassiumtetrakis(pentafluorophenyl)borate,4-(tris(pentafluorophenyOborate)-2,3,5,6-tetrafluoropyridinium, solidiumtetrakis(perfluorophenyl)aluminate, potassiumterakis(pentafluorophenyl), and N,N-dimethylaniliniumtetrakis(perfluorophenyl)aluminate.

In a preferred embodiment, the activator comprises a triaryl carbonium(such as triphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate).

In another embodiment, the activator comprises one or more oftrialkylammonium tetrakis(pentafluorophenyl)borate, N,N-dialkylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate, trialkylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl) borate, N,N-dialkylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, trialkylammoniumtetrakis(perfluoronaphthyl)borate, N,N-dialkylaniliniumtetrakis(perfluoronaphthyl)borate, trialkylammoniumtetrakis(perfluorobiphenyl)borate, N,N-dialkylaniliniumtetrakis(perfluorobiphenyl)borate, trialkylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dialkyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, di-(i-propyl)ammoniumtetrakis(pentafluorophenyl)borate, (where alkyl is methyl, ethyl,propyl, n-butyl, sec-butyl, or t-butyl).

The typical activator-to-catalyst ratio, e.g., all NCAactivators-to-catalyst ratio is about a 1:1 molar ratio. Alternateranges include from 0.1:1 to 100:1, alternately from 0.5:1 to 200:1,alternately from 1:1 to 500:1 alternately from 1:1 to 1000:1. Aparticularly useful range is from 0.5:1 to 10:1, or 1:1 to 5:1.

Optional Scavengers or Co-Activators

In addition to the activator compounds, scavengers, chain transferagents or co-activators may be used. Aluminum alkyl or organoaluminumcompounds which may be utilized as co-activators include, for example,trimethylaluminum, triethylaluminum, triisobutylaluminum,tri-n-hexylaluminum, tri-n-octylaluminum, and diethyl zinc.

In some embodiments, the catalyst systems will additionally comprise oneor more scavenging compounds. Here, the term “scavenger” means acompound that removes polar impurities from the reaction environment.These impurities adversely affect catalyst activity and stability.Typically, the scavenging compound will be an organometallic compoundsuch as the Group-13 organometallic compounds of U.S. Pat. Nos.5,153,157; 5,241,025; and WO 91/09882; WO 94/03506; WO 93/14132; andthat of WO 95/07941. Exemplary compounds include triethyl aluminum,triethyl borane, tri-iso-butyl aluminum, methyl alumoxane, iso-butylalumoxane, and tri-n-octyl aluminum. Those scavenging compounds havingbulky or C₆-C₂₀ linear hydrocarbyl substituents connected to the metalor metalloid center usually minimize adverse interaction with the activecatalyst. Examples include triethyl aluminum, but more preferably, bulkycompounds such as tri-iso-butyl aluminum, tri-iso-prenyl aluminum, andlong-chain linear alkyl-substituted aluminum compounds, such astri-n-hexyl aluminum, tri-n-octyl aluminum, or tri-n-dodecyl aluminum.When alumoxane is used as the activator, any excess over that needed foractivation will scavenge impurities and additional scavenging compoundsmay be unnecessary. Alumoxanes also may be added in scavengingquantities with other activators, e.g., methylalumoxane,[Me₂HNPh]⁺[B(pfp)₄]⁻ or B(pfp)₃ (perfluorophenyl=pfp=C₆F₅).

Particular aluminum scavengers useful in the invention include thosewhere there is oxygen present. That is, the material per se or thealuminum mixture used as a scavenger, includes an aluminum/oxygenspecies, such as an alumoxane or alkylaluminum oxides, e.g.,dialkyaluminum oxides, such as bis(diisobutylaluminum) oxide. In oneaspect, aluminum containing scavengers can be represented by the formula((R_(z)—Al—)_(y)O—)_(x), wherein z is 1-2, y is 1-2, x is 1-100, and Ris a C₁-C₁₂ hydrocarbyl group. In another aspect, the scavenger has anoxygen to aluminum (O/Al) molar ratio of from about 0.25 to about 1.5,more particularly from about 0.5 to about 1.

Preparation of Mixed Catalyst Systems

The above two metal compound components can be combined to form a mixedcatalyst system. The two or more metal compounds can be added togetherin a desired ratio when combined, contacted with an activator, orcontacted with a support material or a supported activator. The metalcompounds may be added to the mixture sequentially or at the same time.

More complex procedures are possible, such as addition of a first metalcompound to a slurry including a support or a supported activatormixture for a specified reaction time, followed by the addition of thesecond metal compound solution, mixed for another specified time, afterwhich the mixture may be recovered for use in a polymerization reactor,such as by spray drying. Lastly, another additive, such as 1-hexene inabout 10 vol % can be present in the mixture prior to the addition ofthe first metal catalyst compound.

The first metal compound may be supported via contact with a supportmaterial for a reaction time. The resulting supported catalystcomposition may then be mixed with mineral oil to form a slurry, whichmay or may not include an activator. The slurry may then be admixed witha second metal compound prior to introduction of the resulting mixedcatalyst system to a polymerization reactor. The second metal compoundsmay be admixed at any point prior to introduction to the reactor, suchas in a polymerization feed vessel or in-line in a catalyst deliverysystem.

The mixed catalyst system may be formed by combining a first metalcompound (for example a metal compound useful for producing a firstpolymer attribute, such as a high molecular weight polymer fraction orhigh comonomer content) with a support and activator, desirably in afirst diluent such as an alkane or toluene, to produce a supported,activated catalyst compound. The supported activated catalyst compound,either isolated from the first diluent or not, is then combined in oneembodiment with a high viscosity diluent such as mineral or silicon oil,or an alkane diluent comprising from 5 to 99 wt % mineral or silicon oilto form a slurry of the supported metal compound, followed by, orsimultaneous to combining with a second metal compound (for example, ametal compound useful for producing a second polymer attribute, such asa low molecular weight polymer fraction or low comonomer content),either in a diluent or as the dry solid compound, to form a supportedactivated mixed catalyst system (“mixed catalyst system”). The mixedcatalyst system thus produced may be a supported and activated firstmetal compound in a slurry, the slurry comprising mineral or siliconoil, with a second metal compound that is not supported and not combinedwith additional activator, where the second metal compound may or maynot be partially or completely soluble in the slurry. In one embodiment,the diluent consists of mineral oil.

Mineral oil, or “high viscosity diluents,” as used herein refers topetroleum hydrocarbons and mixtures of hydrocarbons that may includealiphatic, aromatic, and/or paraffinic components that are liquids at23° C. and above, and typically have a molecular weight of at least 300amu to 500 amu or more, and a viscosity at 40° C. of from 40 to 300 cStor greater, or from 50 to 200 cSt in a particular embodiment. The term“mineral oil” includes synthetic oils or liquid polymers, polybutenes,refined naphthenic hydrocarbons, and refined paraffins known in the art,such as disclosed in BLUE BOOK 2001, MATERIALS, COMPOUNDING INGREDIENTS,MACHINERY AND SERVICES FOR RUBBER 189 247 (J. H. Lippincott, D. R.Smith, K. Kish & B. Gordon eds. Lippincott & Peto Inc. 2001). Preferredmineral and silicon oils useful in the present invention are those thatexclude moieties that are reactive with metallocene catalysts, examplesof which include hydroxyl and carboxyl groups.

The diluent may comprise a blend of a mineral, silicon oil, and/or and ahydrocarbon selected from the group consisting of C₁ to C₁₀ alkanes, C₆to C₂₀ aromatic hydrocarbons, C₇ to C₂₁ alkyl-substituted hydrocarbons,and mixtures thereof. When the diluent is a blend comprising mineraloil, the diluent may comprise from 5 to 99 wt % mineral oil. In someembodiments, the diluent may consist essentially of mineral oil.

In one embodiment, the first metal compound is combined with anactivator and a first diluent to form a catalyst slurry that is thencombined with a support material. Until such contact is made, thesupport particles are preferably not previously activated. The firstmetal compound can be in any desirable form such as a dry powder,suspension in a diluent, solution in a diluent, liquid, etc. Thecatalyst slurry and support particles are then mixed thoroughly, in oneembodiment at an elevated temperature, so that both the first metalcompound and the activator are deposited on the support particles toform a support slurry.

After the first metal compound and activator are deposited on thesupport, a second metal compound may then be combined with the supportedfirst metal compound, wherein the second is combined with a diluentcomprising mineral or silicon oil by any suitable means either before,simultaneous to, or after contacting the second metal compound with thesupported first metal compound. In one embodiment, the first metalcompound is isolated form the first diluent to a dry state beforecombining with the second metal compound. Preferably, the second metalcompound is not activated, that is, not combined with any activator,before being combined with the supported first metal compound. Theresulting solids slurry (including both the supported first and secondmetal compounds) is then preferably, mixed thoroughly at an elevatedtemperature.

A wide range of mixing temperatures may be used at various stages ofmaking the mixed catalyst system. For example, in a specific embodiment,when the first metal compound and at least one activator, such asmethylalumoxane, are combined with a first diluent to form a mixture,the mixture is preferably, heated to a first temperature of from 25° C.to 150° C., preferably, from 50° C. to 125° C., more preferably, from75° C. to 100° C., most preferably, from 80° C. to 100° C. and stirredfor a period of time from 30 seconds to 12 hours, preferably, from 1minute to 6 hours, more preferably, from 10 minutes to 4 hours, and mostpreferably, from 30 minutes to 3 hours.

Next, that mixture is combined with a support material to provide afirst support slurry. The support material can be heated, or dehydratedif desired, prior to combining. In one or more embodiments, the firstsupport slurry is mixed at a temperature greater than 50° C.,preferably, greater than 70° C., more preferably, greater than 80° C.and most preferably, greater than 85° C., for a period of time from 30seconds to 12 hours, preferably, from 1 minute to 6 hours, morepreferably, from 10 minutes to 4 hours, and most preferably, from 30minutes to 3 hours. Preferably, the support slurry is mixed for a timesufficient to provide a collection of activated support particles thathave the first metal compound deposited thereto. The first diluent canthen be removed from the first support slurry to provide a driedsupported first catalyst compound. For example, the first diluent can beremoved under vacuum or by nitrogen purge.

Next, the second metal compound is combined with the activated firstmetal compound in the presence of a diluent comprising mineral orsilicon oil in one embodiment. Preferably, the second metal compound isadded in a molar ratio to the first metal compound in the range from 1:1to 3:1. Most preferably, the molar ratio is approximately 1:1. Theresultant slurry (or first support slurry) is preferably, heated to afirst temperature from 25° C. to 150° C., preferably, from 50° C. to125° C., more preferably, from 75° C. to 100° C., most preferably, from80° C. to 100° C. and stirred for a period of time from 30 seconds to 12hours, preferably, from 1 minute to 6 hours, more preferably, from 10minutes to 4 hours, and most preferably, from 30 minutes to 3 hours.

The first diluent is an aromatic or alkane, preferably, hydrocarbondiluent having a boiling point of less than 200° C. such as toluene,xylene, hexane, etc., may be removed from the supported first metalcompound under vacuum or by nitrogen purge to provide a supported mixedcatalyst system. Even after addition of the oil and/or the second (orother) catalyst compound, it may be desirable to treat the slurry tofurther remove any remaining solvents such as toluene. This can beaccomplished by an N₂ purge or vacuum, for example. Depending upon thelevel of mineral oil added, the resultant mixed catalyst system maystill be a slurry or may be a free flowing powder that comprises anamount of mineral oil. Thus, the mixed catalyst system, while a slurryof solids in mineral oil in one embodiment, may take any physical formsuch as a free flowing solid. For example, the mixed catalyst system mayrange from 1 to 99 wt % solids content by weight of the mixed catalystsystem (mineral oil, support, all catalyst compounds and activator(s))in one embodiment. The metallocene compound may be the first or secondcompound, typically the second compound.

Polymerization Process

The polyethylene compositions of the invention may be prepared by apolymerization processes where monomer (such as ethylene), and,optionally, comonomer (such as hexene), are contacted with a supportedcatalyst system; e.g. the catalyst system including an unbridged hafniummetallocene compound, an unbridged zirconium metallocene compound, anactivator, and a support material as described above.

Monomers useful herein include substituted or unsubstituted C₂ to C₄₀alpha olefins, preferably, C₂ to C₂₀ alpha olefins, preferably, C₂ toC₁₂ alpha olefins, preferably, ethylene, propylene, butene, pentene,hexene, heptene, octene, nonene, decene, undecene, dodecene and isomersthereof. In a preferred embodiment of the invention, the monomerscomprise ethylene and, optional, comonomers comprising one or more C₃ toC₄₀ olefins, preferably, C₄ to C₂₀ olefins, or preferably, C₆ to C₁₂olefins. The C₃ to C₄₀ olefin monomers may be linear, branched, orcyclic. The C₃ to C₄₀ cyclic olefins may be strained or unstrained,monocyclic or polycyclic, and may, optionally, include heteroatomsand/or one or more functional groups.

Exemplary C₃ to C₄₀ comonomers include propylene, butene, pentene,hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene,norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene,cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene,7-oxanorbornadiene, substituted derivatives thereof, and isomersthereof, preferably, hexene, heptene, octene, nonene, decene, dodecene,cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene,1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene,dicyclopentadiene, norbornene, norbornadiene, and their respectivehomologs and derivatives.

In a particular embodiments, one or more dienes are present in thepolymer produced herein at up to 10 wt %, preferably, at 0.00001 to 1.0wt %, preferably, 0.002 to 0.5 wt %, even more preferably, 0.003 to 0.2wt %, based upon the total weight of the composition. In someembodiments 500 ppm or less of diene is added to the polymerization,preferably, 400 ppm or less, preferably, or 300 ppm or less. In otherembodiments, at least 50 ppm of diene is added to the polymerization, or100 ppm or more, or 150 ppm or more.

Particular diolefin monomers useful in this invention include anyhydrocarbon structure, preferably, C₄ to C₃₀, having at least twounsaturated bonds, wherein at least two of the unsaturated bonds arereadily incorporated into a polymer by either a stereospecific or anon-stereospecific catalyst(s). It is further desirable that thediolefin monomers be selected from alpha, omega-diene monomers (i.e.,di-vinyl monomers). In particular, the diolefin monomers are lineardi-vinyl monomers, most preferably, those containing from 4 to 30 carbonatoms. Examples of dienes include butadiene, pentadiene, hexadiene,heptadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene,tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene,heptadecadiene, octadecadiene, nonadecadiene, icosadiene,heneicosadiene, docosadiene, tricosadiene, tetracosadiene,pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene,nonacosadiene, triacontadiene, particularly preferred dienes include1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene,1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene,1,13-tetradecadiene, and low molecular weight polybutadienes (Mw lessthan 1000 g/mol). Exemplary cyclic dienes include cyclopentadiene,vinylnorbornene, norbomadiene, ethylidene norbomene, divinylbenzene,dicyclopentadiene or higher ring containing diolefins with or withoutsubstituents at various ring positions.

In particular embodiments, the process includes the polymerization ofethylene and at least one comonomer having from 3 to 8 carbon atoms,preferably, 4 to 8 carbon atoms. The co-monomers may include propylene,1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-hexene and 1-octene,the most preferred being 1-hexene, 1-butene and 1-octene.

In particular embodiments, the co-monomers are selected from the groupconsisting of propylene, 1-butene, 1-pentene, 3-methyl-1-pentene,4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, and combinationsthereof.

Polymerization processes of this invention can be carried out in anymanner known in the art. Any suspension, homogeneous, bulk, solution,slurry, or gas phase polymerization process known in the art can beused. These processes can be run in a batch, semi-batch, or continuousmode. Gas phase polymerization processes and slurry processes arepreferred. (A homogeneous polymerization process is a process where atleast 90 wt % of the product is soluble in the reaction media.) A bulkhomogeneous process is particularly preferred. (A bulk process is aprocess where monomer concentration in all feeds to the reactor is 70vol % or more.) Alternately, no solvent or diluent is present or addedin the reaction medium (except for the small amounts used as the carrierfor the catalyst system or other additives, or amounts typically foundwith the monomer; e.g., propane in propylene).

In another embodiment, the process is a slurry process. As used herein,the term “slurry polymerization process” means a polymerization processwhere a supported catalyst is employed and monomers are polymerized onthe supported catalyst particles. At least 95 wt % of polymer productsderived from the supported catalyst are in granular form as solidparticles (not dissolved in the diluent).

Suitable diluents/solvents for polymerization include non-coordinating,inert liquids. Examples include straight and branched-chainhydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes,isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic andalicyclic hydrocarbons, such as cyclohexane, cycloheptane,methylcyclohexane, methylcycloheptane, and mixtures thereof, such as canbe found commercially (Isopar™); perhalogenated hydrocarbons, such asperfluorided C₄₋₁₀ alkanes, chlorobenzene, and aromatic andalkylsubstituted aromatic compounds, such as benzene, toluene,mesitylene, and xylene. Suitable solvents also include liquid olefins,which may act as monomers or comonomers, including ethylene, propylene,1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene,1-octene, 1-decene, and mixtures thereof.

In a preferred embodiment, aliphatic hydrocarbon solvents are used asthe solvent, such as isobutane, butane, pentane, isopentane, hexanes,isohexane, heptane, octane, dodecane, and mixtures thereof cyclic andalicyclic hydrocarbons, such as cyclohexane, cycloheptane,methylcyclohexane, methylcycloheptane, and mixtures thereof. In anotherembodiment, the solvent is not aromatic, preferably, aromatics arepresent in the solvent at less than 1 wt %, preferably, less than 0.5 wt%, preferably, less than 0 wt % based upon the weight of the solvents.

Gas Phase Polymerization

In one or more embodiments, in a fluidized gas bed process is used forproducing the polyethylene compositions of the invention. Accordingly, agaseous stream containing one or more monomers is continuously cycledthrough a fluidized bed in the presence of a catalyst under reactiveconditions. The gaseous stream is withdrawn from the fluidized bed andrecycled back into the reactor. Simultaneously, polymer product iswithdrawn from the reactor and fresh monomer is added to replace thepolymerized monomer. (See, for example, U.S. Pat. Nos. 4,543,399;4,588,790; 5,028,670; 5,317,036; 5,352,749; 5,405,922; 5,436,304;5,453,471; 5,462,999; 5,616,661; and 5,668,228; all of which are fullyincorporated herein by reference.)

Slurry Phase Polymerization

A slurry polymerization process generally operates between 1 to about 50atmosphere pressure range (15 psi to 735 psi, 103 kPa to 5068 kPa) oreven greater and temperatures in the range of 0° C. to about 120° C. Ina slurry polymerization, a suspension of solid, particulate polymer isformed in a liquid polymerization diluent medium to which monomer andcomonomers, along with catalysts, are added. The suspension includingdiluent is intermittently or continuously removed from the reactor wherethe volatile components are separated from the polymer and recycled,optionally after a distillation, to the reactor. The liquid diluentemployed in the polymerization medium is typically an alkane having from3 to 7 carbon atoms, preferably a branched alkane. The medium employedshould be liquid under the conditions of polymerization and relativelyinert. When a propane medium is used, the process must be operated abovethe reaction diluent critical temperature and pressure. Preferably, ahexane or an isobutane medium is employed.

End Uses

The polyethylene compositions disclosed herein and blends thereof areuseful in such forming operations as film, sheet, and fiber extrusionand co-extrusion as well as blow molding, injection molding, and rotarymolding. Films include blown or cast films formed by co-extrusion or bylamination useful as shrink film, cling film, stretch film, sealingfilms, oriented films, snack packaging, heavy duty bags, grocery sacks,baked and frozen food packaging, medical packaging, industrial liners,membranes, etc., in food-contact and non-food contact applications.Fibers include melt spinning, solution spinning and melt blown fiberoperations for use in woven or non-woven form to make filters, diaperfabrics, medical garments, geotextiles, etc. Extruded articles includemedical tubing, wire and cable coatings, pipe, geomembranes, and pondliners. Molded articles include single and multi-layered constructionsin the form of bottles, tanks, large hollow articles, rigid foodcontainers and toys, etc.

Specifically, any of the foregoing polymers, such as the foregoingethylene copolymers or blends thereof, may be used in mono- ormulti-layer blown, extruded, and/or shrink films. These films may beformed by any number of well-known extrusion or coextrusion techniques,such as a blown bubble film processing technique, wherein thecomposition can be extruded in a molten state through an annular die andthen expanded to form a uni-axial or biaxial orientation melt prior tobeing cooled to form a tubular, blown film, which can then be axiallyslit and unfolded to form a flat film. Films may be subsequentlyunoriented, uniaxially oriented, or biaxially oriented to the same ordifferent extents.

Blends

The polymers produced herein may be further blended with additionalethylene polymers (referred to as “second ethylene polymers” or “secondethylene copolymers”) and use in film, molded part and other typicalpolyethylene applications.

In one aspect of the invention, the second ethylene polymer is selectedfrom ethylene homopolymer, ethylene copolymers, and blends thereof.Useful second ethylene copolymers can comprise one or more comonomers inaddition to ethylene and can be a random copolymer, a statisticalcopolymer, a block copolymer, and/or blends thereof. The method ofmaking the second ethylene polymer is not critical, as it can be made byslurry, solution, gas phase, high pressure or other suitable processes,and by using catalyst systems appropriate for the polymerization ofpolyethylenes, such as Ziegler-Natta-type catalysts, chromium catalysts,metallocene-type catalysts, other appropriate catalyst systems orcombinations thereof, or by free-radical polymerization. In particularembodiments, the second ethylene polymers are made by the catalysts,activators and processes described in U.S. Pat. Nos. 6,342,566;6,384,142; 5,741,563; PCT Publication Nos. WO 03/040201; and WO97/19991. Such catalysts are well known in the art, and are describedin, for example, ZIEGLER CATALYSTS (Gerhard Fink, Rolf Mülhaupt and HansH. Brintzinger, eds., Springer-Verlag 1995); Resconi et al.; and I, IIMETALLOCENE-BASED POLYOLEFINS (Wiley & Sons 2000). Additional usefulsecond ethylene polymers and copolymers are described at paragraph[00118] to [00126] at pages 30 to 34 of PCT/US2016/028271, filed Apr.19, 2016.

Experimental

All manipulations were performed in an inert N₂ purged glove box unlessotherwise stated. All anhydrous solvents were purchased from FisherChemical and were degassed and dried over molecular sieves prior to use.Deuterated solvents were purchased from Cambridge Isotope Laboratoriesand dried over molecular sieves prior to use. n-Butyl lithium (2.5 Msolution in hexane), diphenyllsilyl dichloride (Ph₂SiCl₂), iodomethane,indene, methyllithium (1.6 M solution in diethyl ether), methylmagnesiumbromide (3.0 M solution in diethyl ether) and silver triflate werepurchased from Sigma-Aldrich. Hafnium tetrachloride (HfCl₄) 99+% and(trimethylsilyl)methyl trifluoromethanesulfonate were procured fromStrem Chemicals and TCI America, respectively, and used as received.Potassium cyclopentadienide (KCp) was prepared according to theliterature procedure. 1-Methylindene and lithium-1-methylindene wereprepared according to the literature methods. The ¹H NMR measurementswere recorded on a 400 MHz Bruker spectrometer.

Synthesis of trimethylsilylmethyl cyclopentadiene, Me₃SiCH₂CpH

A neat trimethylsilylmethyl trifluoromethanesulfonate (25.0 g, 105.8mmol) was dissolved in 300 mL of diethyl ether and cooled to −25° C.; tothis a solid potassium cyclopentadienide (11.14 g, 106.9 mmol) wasslowly added over a period of 10-15 minutes. The resulting mixture wasstirred overnight at room temperature. Insoluble materials were filteredout. Volatiles from the reaction mixture were carefully removed underdynamic vacuum to avoid evaporating the volatile trimethylsilylmethylcyclopentadiene, Me₃SiCH₂CpH. The reaction flask (250 mL round bottomflask) and frit with celite were weighted to calculate yield of theproduct after extraction. The crude materials were then extracted intopentane (3×50 mL) and used without any further purification. The yieldis calculated as 15.47 g (95.2%). The ¹H NMR spectrum was recorded forthe crude material to ensure the product formation. ¹H NMR (400 MHz,C6D6): δ −0.05 (9H, s, Si—CH₃), 1.77 (2H, d, J_(HH)=1.2 Hz, Me₃Si—CH₂),2.83 (1H, sex, J_(HH)=1.5 Hz, Cp-CH), 5.80-6.49 (4H, m, Cp-CH) ppm.

Synthesis of Lithium trimethylsilylmethyl cyclopentadienide,Me₃SiCH₂CpLi

A hexane solution of n-butyl lithium (41.5 mL, 103.8 mmol, 2.5 Msolution) was added drop wise to a precooled solution (1:1 mixture ofpentane and diethyl ether, 200 mL) of the Me₃SiCH₂CpH (15.47 g, 101.7mmol), which was prepared above, over a period of 40-50 minutes at −25°C. The resulting mixture was gradually brought to room temperature andthen continuously stirred overnight. Volatiles were removed in vacuo andremaining crude materials were thoroughly washed with pentane. The finalmaterials were dried under vacuum to obtain a colorless crystallinesolid of Me₃SiCH₂CpLi in 13.6 g (84.6%) yield. ¹H NMR (400 MHz, THF-d₈):δ −0.09 (9H, s, Si—CH₃), 1.84 (2H, s, Me₃Si—CH₂), 5.36 (2H, t,J_(HH)=2.6 Hz, Cp-CH), 5.47 (2H, t, J_(HH)=2.6 Hz, Cp-CH) ppm.

Synthesis of Bis-(trimethylsilylmethyl cyclopentadienide)hafniumdichloride, (Me₃SiCH₂Cp)₂HfCl₂

A solid HfCl₄ (1.011 g, 3.16 mmol) was slurried in precooled diethylether (30 mL) at −25° C., and to this the solid Me₃SiCH₂CpLi (1.0 g, 6.3mmol), which was prepared above, was added over a period of 3-5 minutes.The resulting mixture was stirred overnight at room temperature. Allvolatiles were removed in vacuo and the crude materials weresubsequently extracted into dichloromethane. Solvents were removed underreduced pressure resulted spectroscopically pure (Me₃SiCH₂Cp)₂HfCl₂ as acolorless solid in 1.13 g (70%) yield. ¹H NMR (400 MHz C6D6): δ −0.11(18H, s, SiMe₃—CH₃), 2.18 (4H, s, Me₃Si—CH₂), 5.68 (8H, s, Cp-CH) ppm.

Synthesis of Bis-(trimethylsilylmethyl cyclopentadienyl)hafniumdimethyl, (Me₃SiCH₂Cp)₂HfMe₂

An ethereal solution of MeLi (2.56 mL, 4.1 mmol) was added drop wise toa precooled diethyl ether solution of the (Me₃SiCH₂Cp)₂HfCl₂ (1.12 g,2.03 mmol), which was prepared above, over a period of 3-5 minutes at−25° C. The resulting mixture was stirred overnight at room temperatureto ensure completion of the reaction. Insoluble materials were filteredthrough a pad of celite. Volatiles from the filtrate were removed undervacuum. The crude materials were triturated with pentane and thenextracted into pentane, followed by solvent removal afforded a colorlesscrystalline material of (Me₃SiCH₂Cp)₂HfMe₂ in 875 mg (84.2%) yield. ¹HNMR (400 MHz, C₆D₆): δ −0.23 (6H, s, Hf—CH₃), 0.02 (18H, s, SiMe₃—CH₃),1.89 (4H, s, Me₃Si—CH₂), 5.54-5.48 (8H, m, Cp-CH) ppm.

Synthesis of Rac-meso-bis(1-ethyl-indenyl)zirconium dimethyl,(1-EthInd)₂ZrMe₂

In a 500 mL round bottom flask, a solid ZrCl₄ (9.42 g, 40.4 mmol) wasslurried with 250 mL of dimethoxyethane (DME) and cooled to −25° C. Asolid lithium-1-ethyl-indenyl (11.0 g, 80.8 mmol) was added over aperiod of 5-10 minutes. The orange-yellow reaction mixture was graduallywarmed to room temperature and subsequently heated at 80° C. for 1 hourto ensure the formation of bis(1-ethyl-indenyl)zirconium dichloridein-situ. While heating resulting mixture, it was clear at first and thenbyproduct (LiCl) was precipitated out over a course reaction, revealingthe product formation. Without any further purification, reactionmixture of bis(1-ethyl-indenyl)zirconium dichloride was cooled to −25°C., and to this an ethereal solution of methylmagnesium bromide (27.0mL, 80.8 mmol, 3.0 M solution in diethyl ether) was added over a periodof 10-15 minutes. The resulting mixture was slowly turned pale yellowand then maroon over a course of reaction and continuously stirredovernight at room temperature. Volatiles were removed in vacuo. Thecrude materials were then extracted with hexane (50 mL×5), and solventremoval afforded to the formation of (1-EthInd)₂ZrMe₂ as an off-whitesolid in 13.6 g (89%) yield. The ¹H NMR spectrum of final materialintegrated a ˜0.8:1 ratio of rac/meso isomers. ¹H NMR (400 MHz, C₆D₆): δ−1.33 (3H, s, meso), −0.84 (4.77H, s, rac), −0.34 (3H, s, meso), 2.14(11.42H. overlapping s), 5.47-5.42 (6.41H, m), 6.95-6.88 (7.34H, m),7.14-7.06 (3.45H, m), 7.30-7.27 (3.35H, m) ppm.

Preparation of (Me₃SiCH₂Cp)₂HfMe_(2/)(1-EthInd)₂ZrMe₂ Supported Catalyst

To a stirred vessel 1400 g of toluene was added along with 925 g ofmethylaluminoxane (30 wt % in toluene). To this solution 734 g ofES70—875° C. calcined silica was added. The mixture was stirred forthree hours at 100° C. after which the temperature was reduced and thereaction was allowed to cool to ambient temperature.Bis-(trimethylsilylmethyl cyclopentadienyl) hafnium (IV) dimethyl((Me₃SiCH₂Cp)₂HfMe₂) (16.35 g, 32.00 mmol) and bis-ethylindenylzirconium (IV) dimethyl ((1-EthInd)₂ZrMe₂) (3.26 g, 8.00 mmol) were thendissolved in toluene (250 g) and added to the vessel, which was stirredfor two more hours. The mixing speed was then reduced and stirred slowlywhile drying under vacuum for 60 hours, after which 1038 g of lightyellow silica was obtained.

Preparation of (nPrCp)₂HfMe₂/EthInd Supported Catalyst

Supported (nPrCp)₂HfMe₂/EthInd was made according to the generalprocedures described in U.S. Pat. No. 7,179,876 using a methylalumoxanetreated silica (SMAO-ES70—875 C) prepared as follows: In a 4 L stirredvessel in the drybox methylaluminoxane (MAO) (30 wt % in toluene) wasadded along with 2400 g of toluene. This solution was then stirred at 60RPM for 5 minutes. Next, ES-70™ silica (PQ Corporation, Conshohocken,Pa.) that had been calcined at 875° C. was added to the vessel. Thisslurry was heated at 100° C. and stirred at 120 RPM for 3 hours. Thetemperature was then lowered to 25° C. and cooled to temperature over 2hours. Once cooled, the vessel was set to 8 RPM and placed under vacuumfor 72 hours. After emptying the vessel and sieving the supported MAO,1079 g was collected.

Polymerization in Gas-Phase Reactor

Three polymerizations were run employing the(Me₃SiCH₂Cp)₂HfMe₂/(1-EthInd)₂ZrMe₂ supported catalyst (Polymerization1, 2 & 3), and one polymerization was conducted employing the(nPrCp)2HfMe2 supported catalyst (Polymerization 4). Each polymerizationwas performed in an 18.5 foot tall gas-phase fluidized bed reactor witha 10 foot body and an 8.5 foot expanded section. Cycle and feed gaseswere fed into the reactor body through a perforated distributor plate,and the reactor was controlled at 300 psi and 70 mol % ethylene. Thereactor temperature was maintained at 185° F. throughout each of thepolymerizations by controlling the temperature of the cycle gas loop.Each catalyst was delivered in a mineral oil slurry containing 20 wt %supported catalyst. Hydrogen was lowered and hexene was increasedrelative to standard (nPrCp)2HfMe2 catalyst. Specific informationrelevant to each polymerization is provided in Table I below.

TABLE I Polymerization 1 2 3 4 Polymer Product Inventive A Inventive BInventive C Control D PROCESS DATA H2 conc. (molppm) 250 244 205 348C6/C2 Ratio 0.014 0.014 0.013 0.013 (mol %/mol %) Comonomer conc. 0.950.95 0.93 0.90 (mol %) C2 conc. (mol %) 70.0 69.8 69.8 70 Comonomer/C20.080 0.077 0.080 0.079 Flow Ratio H2/C2 Ratio 3.6 3.5 2.9 5.0 (ppm/mol%) Rx. Pressure SP 300 300 300 300 (psig) Reactor Temp 185 185 185 185SP (F.) Avg. Bedweight (lb) 383 377 372 322 Production (lb/hr) 72 74 7070 Residence Time (hr) 5.3 5.1 5.3 4.6 Avg Velocity (ft/s) 2.25 2.252.25 2.25 Catalyst Slurry Feed 16.5 16.5 16.8 5.015 (cc/hr) or Secs/ShotCatalyst Slurry 0.2 0.2 0.2 0.2 Conc. (wt frac.) Catalyst Feed (g/hr)3.111 3.113 3.113 5.015 Cat Activity 10477 10737 9946 6314 (g poly/gcat) Melt Index (MI) 0.98 1.15 0.72 1.04 (g/10 min) HLMI (g/10 min)22.56 28.74 16.15 23.32 HLMI/MI Ratio 22.96 24.88 22.56 22.43 GradientDensity 0.9178 0.9197 0.9175 0.9180 (g/cc) Bulk Density (g/cc) 0.43820.4482 0.4541 0.4487Polymer Properties

The polymer products prepared above were tested for various propertiesusing the techniques described herein. Namely, melt properties weredetermined according to ASTM D 1238 as set forth above. Mw, Mn, Mz,g′_((vis)), RCI,m, CDR,m, and % hexene were obtained from 4D GPCanalysis using the techniques and calculations provided above. T75-T25was measured and calculated using the techniques described hereinrelative to TREF. The results of these tests and manipulations areprovided in Table II below.

TABLE II Polymer Product Inventive A Inventive B Inventive C Control DPROPERTY MI (dg/min) 0.98 1.1 0.72 1.02 MIR 22.96 24.88 22.56 22.4 Mw(g/mol) 115805 115490 124365 121181 Mn (g/mol) 20356 19728 24884 28010Mz (g/mol) 282760 317422 294283 262225 Mz/Mn 13.9 16.1 11.83 9.36 Mw/Mn5.69 5.85 5 4.33 Mz/Mw 2.44 2.75 2.37 2.16 g′ (vis) 1.0 0.98 0.997 1RCI,m (kg/mol) 72.2 94.1 86.1 75 CDR2,m 1.42 1.58 1.47 1.53 Hexene (%)8.3 8.07 8.55 7.88 T₇₅ − T₂₅ (° C.) na na na Na

The polymer products prepared above were analyzed by ¹H NMR to determineinternal unsaturations using the techniques described herein.

TABLE III Polymer Product Inventive A Inventive B Inventive C Control DUnsaturations per 1000 C Vy1 and Vy2 (I) 0.05 0.07 0.06 0.02 Vy5 (T)0.02 0.04 0.03 0.01 Tri-substituted 0.17 0.16 0.17 0.06 olefins (T1)Vinyls (T) 0.02 0.03 0.01 0.01 Vinylidenes (T) 0.02 0.03 0.02 0.01 Totalinternal 0.22 0.23 0.23 0.08 unsaturations Total unsaturations 0.28 0.330.29 0.11

The polymer products were also analyzed using cross-fractionationchromatography to determine Mw₁, Mw₂, Tw₁, and Tw₂ as described above.The results of these tests and manipulations are provided in Table IVbelow. In addition, cross-fractionation chromatography was similarlyperformed and Mw₁, Mw₂, Tw₁, and Tw₂ were obtained for variouscommercially-available polymers to provide further comparative data.

TABLE IV Mw₁/ Tw₁ − (log(Mw₁/Mw₂))/ Polymer Mw₁ Mw₂ Tw₁ Tw₂ Mw₂ Tw₂ (Tw₁− Tw₂) Inventive A 181,658 114,915 65.5 88.6 1.58 −23.0 −0.0086Inventive B na na na na na na na Inventive C 209,287 116,760 67.7 89.61.79 −21.9 −0.0116 Control D na na na na na na na Exceed 1018 163,239156,716 72.4 86.9 1.04 −14.5 −0.0012 (919/1.0/16) Enable 2010 103,550136,434 75.9 82.5 0.76  −6.7 0.0179 (920/1.1/34) Evolue 3010 148,115166,038 60.3 88.4 0.89 −28.1 0.0018 (926/0.8/n.a.) Elite 5400 174,160109,611 62.0 85.8 1.59 −23.8 −0.0085 (918/1.1/32) Dowlex 2045 117,305238,061 66.4 88.0 0.49 −21.6 0.0142 (920/1.0/29) Borstar FB 2230 268,435371,505 53.5 91.4 0.72 −37.9 0.0037 (923/0.2/110)

The polymer Dowlex™ 2045 polyethylene, Borstar™ FB2230 polyethylene,Evolue™ 3010 polyethylene, and Elite™ 5400 polyethylene are commerciallyavailable. Exceed™ 1018 and Enable™ 2010 polyethylenes are obtained fromExxonMobil Chemical Company (Baytown, Tex.).

With reference to FIG. 2, the x-axis represents the value of thedifference between the first and second weight average elutiontemperatures (Tw₁−Tw₂), and the y-axis in a log scale represents theratio of the first weight average molecular weight to the second weightaverage molecular weight (Mw₁/Mw₂). Shown is a semi-log plot of(Mw₁/Mw₂) vs. (Tw₁−Tw₂), which is designed to show the importantdifferences in MWD/SCBD combination among inventive examples (polymers Aand C, as well as Control B) versus commercial benchmarks. Thesedifferences are believed to play a key role in determining the trade-offpattern and/or balance of various performance attributes such asstiffness, toughness and processability.

Blown Film Evaluations

Blown films were extruded on a 2.5 inch Battenfield Gloucester Line(30:1 L:D) equipped with a 6 inch oscillating die. Output rate was 188lb/hr (10 lb/hr/in die circumference) and the die gap was 60 mil. Thetarget film gauge was 1 mil and the BUR ratio was held constant at 2.5.FLH was typically 19-24 inch. A standard “hump” temperature profile wasused where “BZ” is barrel zone:BZ1=310/BZ2=410/BZ3=380/BZ4=350/BZ5=350/Adapter=390/Die=390 F. Furtherprocess data is found in Table V, which includes film properties at 1.0mil gauge.

TDA is the total defect area, which is a measure of defects in a filmspecimen and is reported as the accumulated area of defects in squaremillimeters (mm²) normalized by the area of film in square meters (m²)examined, thus having a unit of (mm²/m²) or “ppm”. Only defects with adimension above 200 microns are reported in Table V. TDA is obtained byan Optical Control System (OCS). This system includes a small extruder(ME20 2800), cast film die, chill roll unit (Model CR-9), a windingsystem with good film tension control, and an on-line camera system(Model FSA-100) to examine the cast film generated for optical defects.The typical testing condition for the cast film generation includes anextruder zone temperature setting of 154-210° C.; a feed throat/Zone1/Zone 2/Zone 3/Zone4/Die of 70/190/200/210/215/215; an extruder speedof 50 rpm; a chill roll temperature of 30° C.; and a chill roll speed of3.5 m/min. The system generates a cast film of about 4.9 inch in widthand a nominal gauge of 2 mil. Melt temperature varies with materials,and is typically around 215° C.

ESO is the energy specific extrusion output (lb/hr) in film extrusionnormalized by the extruder power (hp) consumption and is a measure of amaterial's processability.

TABLE V bPE Inventive A Inventive B Inventive C Control D Lay Flat (in)23.5 23.5 23.5 23.5 Extruder Zone Temp Settings 310, 410, 380, 310, 410,380, 310, 410, 380, — (° F.) 350, 350 350, 350 350, 350 Die/Adap (° F.)390 390 390 397 Melt Temperature (° F.) 410 405 412 397.5 Air Ring, ° F.69.1 64.7 82.6 51.8 Press. (in water) 4.5 4.0 6.5 4 FLH (in) 27 23 18 21Line Speed (fpm) 165 165 168 168 RPM 94 87 61 61 Rates: lb/hr 187 189188 190 lb/hr/RPM 1.99 2.04 3.09 3.11 lb/in die 9.91 9.49 9.92 10.06Head Pressure (psi) 3150 2860 4580 3850 % motor load 39 37.1 66.8 61Horsepower 19 17 21 20 Torque (HP/RPM) 0.207 0.196 0.354 0.323 ESO(lb/HP/hr) 9.66 10.43 8.77 9.65

The physical properties of the films were tested using the techniquesand methodologies described above. In particular, Dart F50, or Dart DropImpact or Dart Impact (DI), was tested pursuant to ASTM D-1709, methodA, using a dart with a phenolic composite head. Puncture resistance wasdetermined according to a modified ASTM D 5748 test using two 0.25 milHDPE slip sheets, and a United SFM-1 testing machine operating at 10in/min. Haze was tested accordance with ASTM D 1003. Gloss at 45° wasdetermined in accordance with ASTM D 2457. And tear resistance wasdetermined according to Elmendorf Tear pursuant to ASTM D 1922 withsamples conditioned at 23°±2° C. and 50±10% relative humidity for 40hours prior to testing. The results of the testing is provided in TableVI below.

TABLE VI Polymer Product Inventive A Inventive B Inventive C Control D12 (g/10 min) 0.98 1.15 0.72 1.02 121 (g/10 min) 22.6 28.74 16.15 23.3MIR 23.0 24.88 22.56 22.4 Density (g/cm3) 0.9178 0.9180 0.9175 0.9180Gauge Mic (mils) Average 1.0 0.95 1.01 0.98 1% Secant (psi) MD 2863132548 29928 26083 TD 32781 37686 36681 31354 Tensile Yield Strength(psi) MD 1460 1524 1439 1412 TD 1570 1557 1596 1395 Tensile Strength(psi) MD 8642 8645 9109 7604 TD 8099 7953 8857 7427 Elmendorf Tear MD(g) 294 239 306 264 TD (g) 537 470 519 473 MD (g/mil) 285 246 303 272 TD(g/mil) 522 511 519 482 Haze (%) 14.8 16.7 11.6 19 Haze-internal (%) 3.03.03 2.36 2.4 Gloss MD 7 7 12 37 TD 7 8 13 34 Dart Drop Method A (g) 866686 890 590 (g/mil) 866 722 881 602 Puncture (Btec probe, B) BreakEnergy 35.45 31.03 37.02 32.17 (in-lbs/mil)

FIG. 3 shows the average MD/TD film modulus as a function of resindensity for the samples. Within FIG. 3, the dashed line represents alinear regression of the modulus dependence on resin density for twocommercially-available resins, which were obtained under the tradenamesExceed 1018 and Exceed 1327 (ExxonMobil). The equation, AverageModulus=C1*Density−C2, shows the film modulus dependence of thecommercially-available polyethylene compositions as a function of resindensity. C1 is the slope of the linear regression of the modulusdependence on resin density of these polyethylene resins, and C2 is theintercept of this linear regression. As shown in FIG. 3, Inventive A, B,and C exhibited a substantial advantage in film stiffness at a givenresin density when compared to the commercially-available polyethylenecompositions, as well as Control D.

All documents described herein are incorporated by reference herein,including any priority documents and/or testing procedures to the extentthey are not inconsistent with this text. As is apparent from theforegoing general description and the specific embodiments, while formsof the invention have been illustrated and described, variousmodifications can be made without departing from the spirit and scope ofthe invention. Accordingly, it is not intended that the invention belimited thereby. Likewise, the term “comprising” is consideredsynonymous with the term “including.” Likewise whenever a composition,an element or a group of elements is preceded with the transitionalphrase “comprising,” it is understood that we also contemplate the samecomposition or group of elements with transitional phrases “consistingessentially of,” “consisting of,” “selected from the group of consistingof,” or “I” preceding the recitation of the composition, element, orelements and vice versa, e.g., the terms “comprising,” “consistingessentially of,” “consisting of” also include the product of thecombinations of elements listed after the term.

What is claimed is:
 1. A polyethylene composition comprising: from about 80 wt % to about 99.5 wt % ethylene-derived units; and from about 0.5 to about 20 wt % of alpha-olefin derived units other than ethylene-derived units; wherein the composition has total internal unsaturations (Vy1+Vy2+T1) of from about 0.10 to about 0.40 per 1000 carbon atoms, an MI of from about 0.1 to about 6 g/10 min, an HLMI of from about 5.0 to about 40 g/10 min, a density of from about 0.890 to about 0.940 g/ml, a Tw₁-Tw₂ value of from about −25 to about −20° C., an Mw₁/Mw₂ value of from about 1.2 to about 2.0, an Mw/Mn of from about 4.5 to about 12, an Mz/Mw of from about 2.0 to about 3.0, an Mz/Mn of from about 7.0 to about 20, and a g′_((vis)) greater than 0.90.
 2. The polyethylene composition of claim 1, where said polyethylene composition has a density of from about 0.912 to about 0.917 g/ml.
 3. The polyethylene composition of claim 1, wherein the polyethylene composition has an MIR, defined as the ratio of high load melt index (HLMI, determined per ASTM D1238, 190° C., 21.6 kg load)) to melt index (MI, determined per ASTM D1238, 190° C., 2.16 kg load), of from about 20 to about 40 and an HLMI of from about 7.0 to about 35 g/10 min.
 4. The polyethylene composition of claim 1, wherein the polyethylene composition has a Tw₁-Tw₂ value of from about −24 to about −20.5° C., an Mw₁/Mw₂ value of from about 1.35 to about 1.85, an Mw/Mn of from about 4.7 to about 12, an Mz/Mw of from about 2.2 to about 2.9, an Mz/Mn of from about 10 to about 18, and a g′_((vis)) greater than 0.92.
 5. The polyethylene composition of claim 1, wherein the polyethylene composition has a Tw₁-Tw₂ value of from about −23 to about −21° C., an Mw₁/Mw₂ value of from about 1.5 to about 1.8, an Mw/Mn of from about 4.4 to about 9.5, an Mz/Mw of from about 2.3 to about 2.8, an Mz/Mn of from about 11 to about 17, and a g′_((vis)) greater than 0.94.
 6. The polyethylene composition of claim 1 any of claims 1 to 5, wherein the polyethylene composition has tri-substituted olefins (T1) of from about 0.08 to about 0.35 per 1000 carbon atoms.
 7. The polyethylene composition of claim 1 any of claims 1 to 6, wherein the polyethylene composition has internal unsaturations without carbon substitutions (Vy1+Vy2) of from about 0.02 to about 0.1 per 1000 carbon atoms.
 8. The polyethylene composition of claim 7, where said polyethylene composition is characterized by internal unsaturations without carbon substitutions (Vy1+Vy2) of from about 0.04 to about 0.08 per 1000 carbon atoms.
 9. A blown polyethylene film comprising: a polyethylene composition comprising from about 0.5 to about 20 wt % of alpha-olefin derived units other than ethylene-derived units, with the balance including ethylene-derived units, total internal unsaturations (Vy1+Vy2+T1) of from about 0.10 to about 0.40 per 1000 carbon atoms, an MI of from about 0.1 to about 6 g/10 min, an HLMI of from about 5.0 to about 40 g/10 min, a density of from about 0.890 to about 0.940 g/ml, a Tw₁-Tw₂ value of from about −25 to about −20° C., an Mw₁/Mw₂ value of from about 1.2 to about 2.0, an Mw/Mn of from about 4.5 to about 12, an Mz/Mw of from about 2.0 to about 3.0, an Mz/Mn of from about 7.0 to about 20, and a g′_((vis)) greater than 0.90; wherein the blown film has a Dart Drop Impact (DI) that is greater than 300 g/mil, a haze of less than 30%, and a machine-direction tear resistance that is greater than 120 g/mil.
 10. The blown film of claim 9, wherein the blown film has a Dart Drop Impact (DI) that is greater than 400 g/mil, a haze of less than 20%, and a machine-direction tear resistance that is greater than 130 g/mil.
 11. The blown film of claim 9, wherein the polyethylene composition has a density of from 0.914 to 0.917 g/ml, and where the film has a 1% secant modulus, in the transverse direction, of greater than 30,000 psi.
 12. The blown film of claim 11, wherein the polyethylene composition has a density of from 0.914 to 0.917 g/ml, and where the film has a 1% secant modulus, in the transverse direction, of greater than 32,000 psi.
 13. The blown film of claim 9, wherein the polyethylene composition has a density of from about 0.918 to about 0.921 g/ml, and where the film has a 1% secant modulus, in the transverse direction, of greater than 42,000 psi.
 14. The blown film of claim 13, wherein the polyethylene composition has a density of from about 0.918 to about 0.921 g/ml, and where the film has a 1% secant modulus, in the transverse direction, of greater than 45,000 psi.
 15. The blown film of claim 9, wherein the polyethylene composition has a density from about 0.912 to about 0.917 g/ml.
 16. The blown film of claim 9, wherein the polyethylene composition has an MIR, defined as the ratio of high load melt index (HLMI, determined per ASTM D1238, 190° C., 21.6 kg load) to melt index (MI, determined per ASTM D1238, 190° C., 2.16 kg load), of from about 20 to about 40 and an HLMI of from about 7.0 to about 35 g/10 min.
 17. The blown film of claim 9, wherein the polyethylene composition has a Tw₁-Tw₂ value of from about −24 to about −20.5° C., an Mw₁/Mw₂ value of from about 1.35 to about 1.85, an Mw/Mn of from about 4.7 to about 12, an Mz/Mw of from about 2.2 to about 2.9, an Mz/Mn of from about 10 to about 18, and a g′_((vis)) greater than 0.92.
 18. The blown film of claim 9, wherein the polyethylene composition has a Tw₁-Tw₂ value of from about −23 to about −21° C., an Mw₁/Mw₂ value of from about 1.5 to about 1.8, an Mw/Mn of from about 4.9 to about 9.5, an Mz/Mw of from about 2.3 to about 2.8, an Mz/Mn of from about 11 to about 17, and a g′_((vis)) greater than 0.94.
 19. The blown film of claim 9, wherein the polyethylene composition has tri-substituted olefins (T1) of from about 0.08 to about 0.35 per 1000 carbon atoms.
 20. The blown film of claim 9, wherein the polyethylene composition has internal unsaturations without carbon substitutions (Vy1+Vy2) of from about 0.02 to about 0.1 per 1000 carbon atoms.
 21. The blown film of claim 20, wherein the polyethylene composition has internal unsaturations without carbon substitutions (Vy1+Vy2) of from about 0.04 to about 0.08 per 1000 carbon atoms.
 22. The blown film of claim 9, where the polyethylene composition is prepared by combining a catalyst system with ethylene and an alpha-olefin comonomer other than ethylene, where the catalyst system includes (i) an unbridged hafnium metallocene compound; (ii) an unbridged zirconium metallocene compound; (iii) a support material; and (iv) activator.
 23. The blown film of claim 22, where the catalyst system includes an unbridged bis-cyclopentadienyl hafnium catalyst, an unbridged bis-cyclopentadienyl zirconium catalyst, and an activator, with ethylene and within the range from 0.1 to 5 wt % relative to the weight of all monomers of a C3 to C12 α-olefin at a temperature within the range from 60 to 100° C., wherein the unbridged zirconium metallocene is represented by the following formula (A):

where M* is hafnium; each of R¹, R², R⁴ and R⁵ is independently hydrogen, alkoxide, or C₁ to C₄₀ substituted or unsubstituted hydrocarbyl; R³ is —R¹¹—SiR′₃, where R¹¹ is a C₁ to C₄ hydrocarbyl, and each R′ is independently hydrogen or a C₁ to C₂₀ substituted or unsubstituted hydrocarbyl; each R⁶, R⁷, R⁸, R⁹, and R¹⁰ is independently hydrogen, halide, alkoxide, C₁ to C₄₀ substituted or unsubstituted hydrocarbyl, or —R¹¹—SiR′₃, where R¹¹ is a C₁ to C₄ hydrocarbyl, and each R′ is independently hydrogen or a C₁ to C₂₀ substituted or unsubstituted hydrocarbyl; and each X is independently a univalent anionic ligand, or two Xs are joined to form a metallocyclic ring, or two Xs are joined to form a chelating ligand, a diene ligand, or an alkylidene ligand.
 24. The blown film of claim 23, where R³ and R⁹ are both, independently, —R¹¹—SiR′₃, where R¹¹ is a C₁ to C₄ hydrocarbyl, and each R′ is independently C₁ to C₂₀ substituted or unsubstituted hydrocarbyl.
 25. The blown film of claim 22, where the unbridged zirconium metallocene compound is one or more of: Cp(Ind)ZrCl₂, Me₅Cp(Ind)ZrCl₂, Et₅Cp(Ind)ZrCl₂, n-Pr₅Cp(Ind)ZrCl₂, n-Bu₅Cp(Ind)ZrCl₂, Bz₅Cp(Ind)ZrClz, Cp(1-Me Ind)ZrCl₂, Cp(1-Et Ind)ZrCl₂, Cp(1-n-Pr Ind)ZrCl₂, Cp(1-n-Bu Ind)ZrCl₂, Cp(1-n-Pn Ind)ZrCl₂, Cp(1-n-hx Ind)ZrCl₂, Cp(1-Bz Ind)ZrCl₂, Cp(1-Me₃SiCH₂ Ind)ZrCl₂, Me₅Cp(1-Me Ind)ZrCl₂, Me₅Cp(1-Et Ind)ZrCl₂, Me₅Cp(1-n-Pr Ind)ZrCl₂, Me₅Cp(1-n-Bu Ind)ZrCl₂, Me₅Cp(1-n-Pn Ind)ZrCl₂, Me₅Cp(1-n-hx Ind)ZrCl₂, Me₅Cp(1-Bz Ind)ZrCl₂, Me₅Cp(1-Me₃SiCH₂ Ind)ZrCl₂, Et₅Cp(1-Me Ind)ZrCl₂, Et₅Cp(1-Et Ind)ZrCl₂, Et₅Cp(1-n-Pr Ind)ZrCl₂, Et₅Cp(1-n-Bu Ind)ZrCl₂, Et₅Cp(1-n-Pn Ind)ZrCl₂, Et₅Cp(1-n-hx Ind)ZrCl₂, Et₅Cp(1-Bz Ind)ZrCl₂, Et₅Cp(1-Me₃SiCH₂ Ind)ZrCl₂, n-Pr₅Cp(1-Me Ind)ZrCl₂, n-Pr₅Cp(1-Et Ind)ZrCl₂, n-Pr₅Cp(1-n-Pr Ind)ZrCl₂, n-Pr₅Cp(1-n-Bu Ind)ZrCl₂, n-Pr₅Cp(1-n-Pn Ind)ZrCl₂, n-Pr₅Cp(1-n-hx Ind)ZrCl₂, n-Pr₅Cp(1-Bz Ind)ZrCl₂, n-Pr₅Cp(1-Me₃SiCH₂ Ind)ZrCl₂, n-Bu₅CP(1-Me Ind)ZrCl₂, n-Bu₅Cp(1-Et Ind)ZrCl₂, n-Bu₅Cp(1-n-Pr Ind)ZrCl₂, n-Bu₅Cp(1-n-Bu Ind)ZrCl₂, n-Bu₅Cp(1-n-Pn Ind)ZrCl₂, n-Bu₅Cp(1-n-hx Ind)ZrCl₂, n-Bu₅Cp(1-Bz Ind)ZrCl₂, n-Bu₅Cp(1-Me₃SiCH₂ Ind)ZrCl₂, Bz₅Cp(1-Me Ind)ZrCl₂, Bz₅Cp(1-Et Ind)ZrCl₂, Bz₅Cp(1-n-Pr Ind)ZrCl₂, Bz₅Cp(1-n-Bu Ind)ZrCl₂, Bz₅Cp(1-n-Pn Ind)ZrCl₂, Bz₅Cp(1-n-hx Ind)ZrCl₂, Bz₅Cp(1-Bz Ind)ZrCl₂, Bz₅Cp(1-Me₃SiCH₂ Ind)ZrCl₂, and the alkyl or halide versions thereof where the Cl₂ is substituted with Bz₂, Et₂, Me₂, Br₂, I₂, or Ph₂; and wherein the unbridled hafnium metallocene compound generates hydrogen. 